Aromatic polycarbonate resin, process for producing the same, optical-part molding material, and optical part

ABSTRACT

The present invention relates to an aromatic polycarbonate resin which comprises repetitive units originating in residual groups of a 2,2-bis(4-hydroxyphenyl)adamantane compound and a 1,3-bis(4-hydroxyphenyl)adamantane compound having a substituent on an aromatic ring and which is excellent in a transparency, a heat resistance and a mechanical strength and has a good moldability and a production process for the aromatic polycarbonate resin described above in which the adamantane compounds described above are reacted with a carbonic ester-forming compound. Further, it relates to an aromatic polycarbonate resin which is excellent in an optical characteristic and an optical part prepared by molding the same.

TECHNICAL FIELD

The present invention comprises the first invention, the secondinvention and the third invention, and the first invention and thesecond invention relate to an aromatic polycarbonate resin and aproduction process for the same, more specifically to an aromaticpolycarbonate resin which is excellent in a transparency, a heatresistance and a mechanical strength and which has a good moldabilityand an effective production process for the same. The third inventionrelates to an optical part-molding material and an optical part, morespecifically to an optical part-molding material suited to a moldingmaterial for an optical disc substrate such as a digital audio disc, adigital video disc and an optical memory disc, various lenses such as alens for an optical pickup, spectacle lenses, contact lenses and a lenssheet, an optical sheet substrate such as a prism, a mirror, an opticalfiber, a liquid crystal display and a portable key sheet and an opticalfunctional element such as a light guiding substance, a reflection film,a light scattering sheet, a polarizing plate and a phase differenceplate and an optical part prepared by molding the same.

BACKGROUND ART

Referring to the first invention and the second invention, an aromaticpolycarbonate resin is excellent in properties such as a transparency, aheat resistance and a mechanical strength, and therefore it is widelyused as a so-called engineering plastic in various industrial fields. Ingeneral, an aromatic polycarbonate resin produced by reacting2,2-bis(4-hydroxyphenyl)propane (common name: bisphenol A) with acarbonic ester-forming compound such as phosgene and diphenyl carbonateis used as the above aromatic polycarbonate resin. Because of a goodbalance of a transparency and a mechanical strength with a moldability,an aromatic polycarbonate resin produced using this bisphenol A as a rawmaterial is used as a raw material for electric and electronicequipments and optical equipments in many cases. In recent years, theseequipments are increasingly demanded to be decreased in a size and aweight, and an aromatic polycarbonate resin which is further improved incharacteristics such as a heat resistance and a mechanical strengthwithout reducing basic characteristics endowed to this aromaticpolycarbonate resin is requested to be developed in order to meet theabove demand.

Then, in order to meet the above demand, it has been tried to obtain anaromatic polycarbonate resin which is improved further more in a heatresistance and a mechanical strength by using compounds having variousstructures as a divalent phenol which is a raw material for an aromaticpolycarbonate resin. For example, an aromatic polycarbonate resin usinga raw material of a bisphenol derivative of adamantane as divalentphenol is proposed in Soobsch. Akad. Nauk Gruz. SSR (1977), 88(3), p.597 to 600. This aromatic polycarbonate resin in which an adamantaneskeleton is introduced into a structural unit of an aromaticpolycarbonate polymer chain has a high heat resistance but has thedifficulties that it has a poor solubility in solvents because it isliable to be crystallized and it is inferior in a moldability and thatthe molded article is reduced in a transparency. Further, proposed arearomatic polycarbonate resins using a raw material of1,1-bis(4-hydroxyphenyl)cyclohexane and9,9′-bis(4-hydroxyphenyl)fluorene alone or in combination with bisphenolA as divalent phenol. However, these aromatic polycarbonate resinscomprising a structural unit having a residue of divalent phenol has ahigher heat resistance than that of an aromatic polycarbonate resinusing bisphenol A as a raw material, but further higher heat resistanceis required in the production steps of electric and electronic equipmentparts. Thus, when used as a raw material for electric and electronicequipments and optical equipment parts, an aromatic polycarbonate resinwhich has further higher transparency, heat resistance and mechanicalstrength and which is excellent in a moldability is required to bedeveloped.

An object of the first invention and the second invention is to providean aromatic polycarbonate resin which is excellent in a transparency, aheat resistance and a mechanical strength and which has a goodmoldability and a production process for the same.

Referring to the third invention, various plastics are proposed as anoptical part-molding material. Characteristics such as a heatresistance, an impact resistance, a mechanical strength and an opticalproperty are required to the above optical part-molding material, andengineering plastics such as polymethyl methacrylate, polycarbonateusing 2,2-bis(4-hydroxyphenyl)propane as a raw material, polyacrylateand polyethersulfone have so far been used as materials satisfying theabove requirements.

On the other hand, some of a large number of these optical parts have ahigh transparency and require a very high heat resistance. For example,a liquid crystal display substrate of an active matrix mode in which athin film transistor is arranged as a switching element for everypicture element on a glass substrate in a matrix form and actuated isadopted in many cases. In a production step of the above liquid crystaldisplay, an electrical insulating layer of silicon nitride has to beformed by a glow discharge deposition method when forming a thin filmtransistor on a substrate. Accordingly, since the substrate of the aboveliquid crystal display is glass, it is liable to be broken by impactexerted from the outside such as falling, and therefore it is desired touse a substrate of an engineering plastic having an excellent impactresistance. In the above engineering plastics, however, a heatresistance and an impact resistance are not satisfactory in, forexample, polymethyl methacrylate, and a heat resistance in forming anelectrical insulating layer is not necessarily satisfactory inpolycarbonate and polyacrylate. Further, polyethersulfone has thedifficulties that it has a high heat resistance but is colored amber andthat optical anisotropy is liable to be brought about by slightmolecular orientation.

Thus, an optical part-molding material which is excellent in a heatresistance and a mechanical strength in addition to an opticalcharacteristic is requested to be developed as a molding material foroptical parts.

An object of the third invention is to provide an optical part-moldingmaterial which is excellent in an optical characteristic and amechanical strength and which has a particularly high heat resistanceand an optical part prepared by molding the same.

DISCLOSURE OF THE INVENTION

I. First Invention

Intensive researches repeated by the present inventors in order to solvethe problems described above have resulted in finding that the objectdescribed above can be achieved by an aromatic polycarbonate resinobtained by reacting specific divalent phenols having an adamantaneskeleton and divalent phenols having various chemical structures with acarbonic ester-forming compound, and they have come to complete thepresent first invention based on the above knowledge.

That is, the essential point of the first invention is described below.

-   (1) An aromatic polycarbonate resin which comprises a repetitive    unit (I-1) represented by the following Formula [I-1]:    (wherein R¹ represents a group selected from the group of a halogen    atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group    having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon    atoms, an aryl-substituted alkenyl group having 7 to 13 carbon atoms    and a fluoroalkyl group having 1 to 6 carbon atoms; R² represents a    group selected from the group of a halogen atom, an alkyl group    having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon    atoms, an aryl group having 6 to 12 carbon atoms, an    aryl-substituted alkenyl group having 7 to 13 carbon atoms and a    fluoroalkyl group having 1 to 12 carbon atoms; m represents an    integer of 0 to 4; and n represents an integer of 0 to 14) and a    repetitive unit (I-2) represented by the following Formula [I-2]:    (wherein R³ represents a group selected from the group of a halogen    atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group    having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon    atoms, an aryl-substituted alkenyl group having 7 to 13 carbon atoms    and a fluoroalkyl group having 1 to 12 carbon atoms; X represents a    single bond, —O—, —CO—, —S—, —SO—, —SO₂—, —C(R⁴R⁵)— (provided that    R⁴ and R⁵ each represent independently a hydrogen atom, an alkyl    group having 1 to 6 carbon atoms, a phenyl group or a    trifluoromethyl group), a substituted or non-substituted    cycloalkylidene group having 6 to 12 carbon atoms, a    9,9′-fluorenylidene group, a 1,8-menthanediyl group, a    2,8-menthanediyl group, a substituted or non-substituted    pyrazylidene group, a substituted or non-substituted arylene group    having 6 to 12 carbon atoms or —C(CH₃)₂—ph—C(CH₃)₂— (provided that    ph represents a phenylene group); and p represents an integer of 0    to 4) and in which the solution having a concentration of 0.5    g/deciliter using methylene chloride as a solvent has a reduced    viscosity (η_(sp)/c) of 0.1 deciliter/g or more which is measured at    20° C.-   (2) The aromatic polycarbonate resin as described in the above item    (1), wherein the repetitive unit (I-2) is represented by the    following Formula [I-3]:    wherein R³, X and p each represent the same as R³, X and p in    Formula [I-2].-   (3) The aromatic polycarbonate resin as described in the above    item (1) or (2), wherein R¹ in Formula [I-1] is an alkyl group    having 1 to 6 carbon atoms.-   (4) The aromatic polycarbonate resin as described in any of the    above items (1) to (3), wherein X in Formula [I-2] is —C(R⁴R⁵)—    (provided that R⁴ and R⁵ each represent independently a hydrogen    atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a    trifluoromethyl group), a substituted or non-substituted    cycloalkylidene group having 6 to 12 carbon atoms or a    9,9′-fluorenylidene group.-   (5) A production process for the aromatic polycarbonate resin as    described in the above item (1), characterized by reacting a    2,2-bis(4-hydroxyphenyl)adamantane compound represented by the    following Formula [I-4]:    (wherein R¹ represents a group selected from the group of a halogen    atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group    having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon    atoms, an aryl-substituted alkenyl group having 7 to 13 carbon atoms    and a fluoroalkyl group having 1 to 6 carbon atoms; R² represents a    group selected from the group of a halogen atom, an alkyl group    having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon    atoms, an aryl group having 6 to 12 carbon atoms, an    aryl-substituted alkenyl group having 7 to 13 carbon atoms and a    fluoroalkyl group having 1 to 12 carbon atoms; m represents an    integer of 0 to 4; and n represents an integer of 0 to 14) and    divalent phenol represented by the following Formula [I-5]:    (wherein R³ represents a group selected from the group of a halogen    atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group    having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon    atoms, an aryl-substituted alkenyl group having 7 to 13 carbon atoms    and a fluoroalkyl group having 1 to 12 carbon atoms; X represents a    single bond, —O—, —CO—, —S—, —SO—, —SO₂—, —C(R⁴R⁵)— (provided that    R⁴ and R⁵ each represent independently a hydrogen atom, an alkyl    group having 1 to 6 carbon atoms, a phenyl group or a    trifluoromethyl group), a substituted or non-substituted    cycloalkylidene group having 6 to 12 carbon atoms, a    9,9′-fluorenylidene group, a 1,8-menthanediyl group, a    2,8-menthanediyl group, a substituted or non-substituted    pyrazylidene group, a substituted or non-substituted arylene group    having 6 to 12 carbon atoms or —C(CH₃)₂-ph-C(CH₃)₂— (provided that    ph represents a phenylene group); and p represents an integer of 0    to 4) with a carbonic ester-forming compound.-   (6) The production process for the aromatic polycarbonate resin as    described in the above item (5), wherein a compound represented by    the following Formula [I-6] is used as the divalent phenol:    wherein R³, X and p each represent the same as R³, X and p in    Formula [I-5].-   (7) The production process for the aromatic polycarbonate resin as    described in the above item (5) or (6), wherein the compound in    which R¹ in Formula [I-4] is an alkyl group having 1 to 6 carbon    atoms is used as the 2,2-bis(4-hydroxyphenyl)adamantane compound.-   (8) The production process for the aromatic polycarbonate resin as    described in any of the above items (5) to (7), wherein used as the    divalent phenol is the compound in which X in Formula [I-5] is    —C(R⁴R⁵)— (provided that R⁴ and R⁵ each represent independently a    hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl    group or a trifluoromethyl group), a substituted or non-substituted    cycloalkylidene group having 6 to 12 carbon atoms or a    9,9′-fluorenylidene group.    II. Second Invention

Intensive researches repeated by the present inventors in order to solvethe problems described above have resulted in finding that the objectdescribed above can be achieved by an aromatic polycarbonate resinobtained by reacting specific divalent phenols having an adamantaneskeleton and constituted by a phenol group having a substituent with acarbonic ester-forming compound, and they have come to complete thepresent second invention based on the above knowledge.

That is, the essential point of the second invention is described below.

-   (1) An aromatic polycarbonate resin which comprises a repetitive    unit represented by the following Formula [II-1]:    (wherein R¹ represents a group selected from the group of a halogen    atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group    having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon    atoms, an aryl-substituted alkenyl group having 7 to 13 carbon atoms    and a fluoroalkyl group having 1 to 6 carbon atoms; and m represents    an integer of 1 to 4) and in which the solution having a    concentration of 0.5 g/deciliter using methylene chloride as a    solvent has a reduced viscosity (η_(sp)/c) of 0.1 deciliter/g or    more which is measured at 20° C.-   (2) The aromatic polycarbonate resin as described in the above item    (1), wherein R¹ in Formula [II-1] is an alkyl group having 1 to 6    carbon atoms.-   (3) An aromatic polycarbonate resin which comprises a repetitive    unit (II-1) represented by the following Formula [II-2]:    (wherein R² represents a group selected from the group of a halogen    atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group    having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon    atoms, an aryl-substituted alkenyl group having 7 to 13 carbon atoms    and a fluoroalkyl group having 1 to 6 carbon atoms; and n is an    integer of 1 to 4) and a repetitive unit (II-2) represented by the    following Formula [II-3]:    (wherein R³ represents a group selected from the group of a halogen    atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group    having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon    atoms, an aryl-substituted alkenyl group having 7 to 13 carbon atoms    and a fluoroalkyl group having 1 to 12 carbon atoms; X represents a    single bond, —O—, —CO—, —S—, —SO—, —SO₂—, —C(R⁴R⁵)— (provided that    R⁴ and R⁵ each represent independently a hydrogen atom, an alkyl    group having 1 to 6 carbon atoms, a phenyl group or a    trifluoromethyl group), a substituted or non-substituted    cycloalkylidene group having 6 to 12 carbon atoms, a    9,9′-fluorenylidene group, a 1,8-menthanediyl group, a    2,8-menthanediyl group, a substituted or non-substituted    pyrazylidene group, a substituted or non-substituted arylene group    having 6 to 12 carbon atoms or —C(CH₃)₂-ph-C(CH₃)₂— (provided that    ph represents a phenylene group); and p represents an integer of 0    to 4) and in which the solution having a concentration of 0.5    g/deciliter using methylene chloride as a solvent has a reduced    viscosity (η_(sp)/c) of 0.1 deciliter/g or more which is measured at    20° C.-   (4) The aromatic polycarbonate resin as described in the above item    (3), wherein the repetitive unit (II-2) is represented by the    following Formula [II-4]:    wherein R³, X and p each represent the same as R³, X and p in    Formula [II-3].-   (5) The aromatic polycarbonate resin as described in the above    item (3) or (4), wherein R² in Formula [II-2] is an alkyl group    having 1 to 6 carbon atoms.-   (6) The aromatic polycarbonate resin as described in any of the    above items (3) to (5), wherein X in Formula [II-3] is —C(R⁴R⁵)—    (provided that R⁴ and R⁵ each represent independently a hydrogen    atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a    trifluoromethyl group), a substituted or non-substituted    cycloalkylidene group having 6 to 12 carbon atoms or a    9,9′-fluorenylidene group.-   (7) A production process for the aromatic polycarbonate resin as    described in the above item (1), characterized by reacting a    1,3-bis(4-hydroxyphenyl)adamantane compound represented by the    following Formula [II-5]:    (wherein R¹ represents a group selected from the group of a halogen    atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group    having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon    atoms, an aryl-substituted alkenyl group having 7 to 13 carbon atoms    and a fluoroalkyl group having 1 to 6 carbon atoms; and m represents    an integer of 1 to 4) with a carbonic ester-forming compound.-   (8) The production process for the aromatic polycarbonate resin as    described in the above item (7), wherein the compound in which R¹ in    Formula [II-5] is an alkyl group having 1 to 6 carbon atoms is used    as the 1,3-bis(4-hydroxyphenyl)adamantane compound.-   (9) A production process for the aromatic polycarbonate resin as    described in the above item (3), characterized by reacting a    1,3-bis(4-hydroxyphenyl)adamantane compound represented by the    following Formula [II-6]:    (wherein R² represents a group selected from the group of a halogen    atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group    having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon    atoms, an aryl-substituted alkenyl group having 7 to 13 carbon atoms    and a fluoroalkyl group having 1 to 6 carbon atoms; and n represents    an integer of 1 to 4) and divalent phenol represented by the    following Formula [II-7]:    (wherein R³ represents a group selected from the group of a halogen    atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group    having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon    atoms, an aryl-substituted alkenyl group having 7 to 13 carbon atoms    and a fluoroalkyl group having 1 to 12 carbon atoms; X represents a    single bond, —O—, —CO—, —S—, —SO—, —SO₂—, —C(R⁴R⁵)— (provided that    R⁴ and R⁵ each represent independently a hydrogen atom, an alkyl    group having 1 to 6 carbon atoms, a phenyl group or a    trifluoromethyl group), a substituted or non-substituted    cycloalkylidene group having 6 to 12 carbon atoms, a    9,9′-fluorenylidene group, a 1,8-menthanediyl group, a    2,8-menthanediyl group, a substituted or non-substituted    pyrazylidene group, a substituted or non-substituted arylene group    having 6 to 12 carbon atoms or —C(CH₃)₂-ph-C(CH₃)₂— (provided that    ph represents a phenylene group); and p represents an integer of 0    to 4) with a carbonic ester-forming compound.-   (10) The production process for the aromatic polycarbonate resin as    described in the above item (9), wherein the compound in which R² in    Formula [II-6] is an alkyl group having 1 to 6 carbon atoms is used    as the 1,3-bis(4-hydroxyphenyl)adamantane compound.-   (11) The production process for the aromatic polycarbonate resin as    described in the above item (9) or (10), wherein a compound    represented by the following Formula [II-8] is used as the divalent    phenol:    wherein R³, X and p each represent the same as R³, X and p in    Formula [II-7].-   (12) The production process for the aromatic polycarbonate resin as    described in any of the above items (9) to (11), wherein used as the    divalent phenol is the compound in which X in Formula [II-7] is    —C(R⁴R⁵)— (provided that R⁴ and R⁵ each represent independently a    hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl    group or a trifluoromethyl group), a substituted or non-substituted    cycloalkylidene group having 6 to 12 carbon atoms or a    9,9′-fluorenylidene group.    III. Third Invention

Intensive researches repeated by the present inventors in order to solvethe problems described above have resulted in finding that the objectdescribed above can be achieved by using an aromatic polycarbonate resincomprising a repetitive unit having a specific adamantane skeletoncontaining a 2,2-adamantyl group as an optical part-molding material,and they have come to complete the present third invention based on theabove knowledge.

That is, the essential point of the third invention is described below.

-   (1) An optical part-molding material comprising an aromatic    polycarbonate resin which comprises a repetitive unit represented by    the following Formula [III-1]:    (wherein R¹ and R² each represent independently a group selected    from the group of a halogen atom, an alkyl group having 1 to 6    carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl    group having 6 to 12 carbon atoms, an aryl-substituted alkenyl group    having 7 to 13 carbon atoms and a fluoroalkyl group having 1 to 6    carbon atoms; R³ represents a group selected from the group of a    halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy    group having 1 to 12 carbon atoms, an aryl group having 6 to 12    carbon atoms, an aryl-substituted alkenyl group having 7 to 13    carbon atoms and a fluoroalkyl group having 1 to 12 carbon atoms; a    and b represent an integer of 0 to 4; and c represents an integer of    0 to 14) and in which the solution having a concentration of 0.5    g/deciliter using methylene chloride as a solvent has a reduced    viscosity (η_(sp)/c) of 0.1 deciliter/g or more which is measured at    20° C.-   (2) The optical part-molding material as described in the above item    (1), wherein R¹ and R² in Formula [III-1] are alkyl groups having 1    to 6 carbon atoms.-   (3) The optical part-molding material comprising the aromatic    polycarbonate resin as described in the above item (1) or (2),    wherein the repetitive unit is represented by the following Formula    [III-2]:    wherein R¹, R², R³, a, b and c each represent the same as R¹, R², R³    a, b and c in Formula [III-1].-   (4) The optical part-molding material as described in the above item    (3), wherein R¹ and R² in Formula [III-2] are alkyl groups having 1    to 6 carbon atoms.-   (5) An optical part-molding material comprising an aromatic    polycarbonate resin which comprises a repetitive unit (III-1)    represented by the following Formula [III-3]:    (wherein R⁴ and R⁵ each represent independently a group selected    from the group of a halogen atom, an alkyl group having 1 to 6    carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl    group having 6 to 12 carbon atoms, an aryl-substituted alkenyl group    having 7 to 13 carbon atoms and a fluoroalkyl group having 1 to 6    carbon atoms; R⁶ represents a group selected from the group of a    halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy    group having 1 to 12 carbon atoms, an aryl group having 6 to 12    carbon atoms, an aryl-substituted alkenyl group having 7 to 13    carbon atoms and a fluoroalkyl group having 1 to 12 carbon atoms; d    and e represent an integer of 0 to 4; and f represents an integer of    0 to 14) and a repetitive unit (III-2) represented by the following    Formula [III-4]:    [wherein R⁷ and R⁸ each represent independently a group selected    from the group of a halogen atom, an alkyl group having 1 to 12    carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl    group having 6 to 12 carbon atoms, an aryl-substituted alkenyl group    having 7 to 13 carbon atoms and a fluoroalkyl group having 1 to 12    carbon atoms; X represents a single bond, —O—, —CO—, —S—, —SO—,    —SO₂—, —C(R⁹R¹⁰)— (provided that R⁹ and R¹⁰ each represent    independently a hydrogen atom, an alkyl group having 1 to 6 carbon    atoms, a phenyl group or a trifluoromethyl group), a substituted or    non-substituted cycloalkylidene group having 6 to 12 carbon atoms, a    9,9′-fluorenylidene group, a 1,8-menthanediyl group, a    2,8-menthanediyl group, a substituted or non-substituted    pyrazylidene group, a substituted or non-substituted arylene group    having 6 to 12 carbon atoms, —C(CH₃)₂-ph-C(CH₃)₂— (provided that ph    represents a phenylene group) or the following Formula [III-5] or    [III-6]:    (wherein R¹¹ and R¹² each represent independently a group selected    from the group of a halogen atom, an alkyl group having 1 to 12    carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl    group having 6 to 12 carbon atoms, an aryl-substituted alkenyl group    having 7 to 13 carbon atoms and a fluoroalkyl group having 1 to 12    carbon atoms; and i and j each represent an integer of 0 to 14); and    g and h each represent an integer of 0 to 4] and in which the    solution having a concentration of 0.5 g/deciliter using methylene    chloride as a solvent has a reduced viscosity (η_(sp)/c) of 0.1    deciliter/g or more which is measured at 20° C.-   (6) The optical part-molding material as described in the above item    (5), wherein R⁴ and R⁵ in Formula [III-3] are alkyl groups having 1    to 6 carbon atoms.-   (7) The optical part-molding material as described in the above    item (5) or (6), wherein the repetitive unit (III-2) is represented    by the following Formula [III-7]:    wherein R⁷, R⁸, X, g and h each represent the same as R⁷, R⁸, X, g    and h in Formula [III-4].-   (8) The optical part-molding material as described in any of the    above items (5) to (7), wherein X in Formula [III-4] is —C(R⁹R¹⁰)—    (provided that R⁹ and R¹⁰ each represent independently a hydrogen    atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a    trifluoromethyl group), a substituted or non-substituted    cycloalkylidene group having 6 to 12 carbon atoms or a    9,9′-fluorenylidene group.-   (9) An optical part prepared by molding the optical part-molding    material as described in any of the above items (1) to (8).

BEST MODE FOR CARRYING OUT THE INVENTION

The embodiment of the present invention shall be explained below.

I. First Invention

The first present invention (hereinafter referred to merely as the┌present invention┘) relates to the aromatic polycarbonate resin whichcomprises the repetitive unit (I-1) represented by Formula [I-1]described above and the repetitive unit (I-2) represented by Formula[I-2] described above and in which the solution having a concentrationof 0.5 g/deciliter using methylene chloride as a solvent has a reducedviscosity (η_(sp)/c) of 0.1 deciliter/g or more which is measured at 20°C.

In the above aromatic polycarbonate resin, the alkyl group having 1 to 6carbon atoms represented by R¹ in Formula [I-1] described above includesmethyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl,tert-butyl, n-pentyl, n-hexyl, cyclopentyl and cyclohexyl. The alkoxygroup having 1 to 6 carbon atoms includes methoxy, ethoxy, n-propoxy,i-propoxy, i-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy andn-hexyloxy. The aryl group having 6 to 12 carbon atoms includes phenyl,biphenyl, triphenyl and naphthyl, and the aryl-substituted alkenyl grouphaving 7 to 13 carbon atoms includes benzyl, phenethyl, styryl andcinnamyl. Further, the fluoroalkyl group having 1 to 6 carbon atomsincludes monofluoromethyl, difluoromethyl and trifluoromethyl.

Among the various substituents represented by R¹ in this Formula [I-1],the alkyl group having 1 to 6 carbon atoms is preferred because of theexcellent heat resistance, and methyl is more preferred. In additionthereto, among the various substituents described above, the preferredones include cyclohexyl, methoxy, phenyl and trifluoromethyl. In theabove Formula [I-1], m may be 0, that is, it may be a hydrogen atom ormay have 1 to 4 substituents. This m is more preferably 0 to 2.

The halogen atom represented by R² in Formula [I-1] described aboveincludes a fluorine atom, a chlorine atom, a bromine atom and an iodineatom. The alkyl group having 1 to 12 carbon atoms represented by R² inthe above formula includes methyl, ethyl, n-propyl, i-propyl, n-butyl,i-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl,n-nonyl, n-decyl, n-undecyl, n-dodecyl, cyclopentyl and cyclohexyl. Thealkoxy group having 1 to 12 carbon atoms includes methoxy, ethoxy,n-propoxy, i-propoxy, i-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy,n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy,n-undecyloxy and n-dodecyloxy. The aryl group having 6 to 12 carbonatoms includes phenyl, biphenyl, triphenyl and naphthyl, and thearyl-substituted alkenyl group having 7 to 13 carbon atoms includesbenzyl, phenethyl, styryl and cinnamyl. Further, the fluoroalkyl grouphaving 1 to 12 carbon atoms includes monofluoromethyl, difluoromethyland trifluoromethyl. Among the above various substituents, the preferredones include methyl, ethyl, methoxy, ethoxy, phenyl and trifluoromethyl.Further, n in the above Formula [I-1] may be 0, that is, it may be onlya hydrogen atom or may have any of 1 to 14 substituents.

In the above aromatic polycarbonate resin, the halogen atom representedby R³ in Formula [I-2] described above includes a fluorine atom, achlorine atom, a bromine atom and an iodine atom. The alkyl group having1 to 12 carbon atoms represented by R³ in the above formula includesmethyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl,tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl,n-undecyl, n-dodecyl, cyclopentyl and cyclohexyl. The alkoxy grouphaving 1 to 12 carbon atoms includes methoxy, ethoxy, n-propoxy,i-propoxy, i-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy, n-hexyloxy,n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy andn-dodecyloxy. The aryl group having 6 to 12 carbon atoms includesphenyl, biphenyl, triphenyl and naphthyl, and the aryl-substitutedalkenyl group having 7 to 13 carbon atoms includes benzyl, phenethyl,styryl and cinnamyl. Further, the fluoroalkyl group having 1 to 12carbon atoms includes monofluoromethyl, difluoromethyl andtrifluoromethyl. Among the above various substituents, the preferredones include methyl, ethyl, cyclohexyl and phenyl.

In the above aromatic polycarbonate resin, the alkyl group having 1 to 6carbon atoms represented by R⁴ and R⁵ in Formula [I-2] described aboveincludes methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl,tert-butyl, n-pentyl and n-hexyl. Among them, the suited ones includemethyl, ethyl and n-propyl. Further, the substituted or non-substitutedcycloalkylidene group having 6 to 12 carbon atoms represented by X inFormula [I-2] includes cyclopentylidene, cyclohexylidene,cycloheptylidene and cyclooctylidene, and the substituted ornon-substituted arylene group having 6 to 12 carbon atoms includesphenylene, biphenylene, 1,4-phenylenebis(1-methylethylidene) and1,3-phenylenebis(1-methylethylidene).

Further, the aromatic polycarbonate resin in which the repetitive unit(I-2) has the structural unit represented by Formula [I-3] is preferredsince it is excellent in a heat resistance and a mechanical strength.The divalent group represented by X in the above Formulas [I-2] and[I-3] is preferably —C(R⁴R⁵)— (provided that R⁴ and R⁵ each representindependently a hydrogen atom, an alkyl group having 1 to 6 carbonatoms, a phenyl group or a trifluoromethyl group), a substituted ornon-substituted cycloalkylidene group having 6 to 12 carbon atoms or a9,9′-fluorenylidene group because of more excellent heat resistance.

A content proportion of the repetitive unit (I-1) represented by Formula[I-1] to the repetitive unit (I-2) represented by Formula [I-2] eachconstituting the above aromatic polycarbonate resin shall notspecifically be restricted, and a content proportion[(I-1)/((I-1)+(I-2))] of the repetitive unit (I-1) to the wholerepetitive units falls preferably in a range of 0.05 to 0.99 in terms ofa mole ratio. This is because of the reasons that if a mole ratio of theabove repetitive unit (I-1) is lower than 0.05, the moldingprocessability is good but the degree of a rise in the heat resistanceis small and that if the above mole ratio is higher than 0.99, theparticularly excellent heat resistance is shown but the moldingprocessability is reduced in a certain case because of the lowsolubility in a solvent. Further, the content proportion of the aboverepetitive unit (I-1) to the whole repetitive units falls particularlypreferably in a range of 0.05 to 0.95 because it provides a good balanceof the heat resistance and the mechanical strength with the moldingprocessability.

The aromatic polycarbonate resin of the present invention comprises therepetitive units (I-1) and (I-2), and the solution having aconcentration of 0.5 g/deciliter using methylene chloride as a solventhas a reduced viscosity (η_(sp)/c) of 0.1 deciliter/g or more which ismeasured at 20° C. If the above reduced viscosity is less than 0.1deciliter/g, the aromatic polycarbonate resin can not sufficientlyobtain a heat resistance and a mechanical strength. The resin in whichthe above reduced viscosity is 0.3 to 3.0 deciliter/g is particularlysuited as a molding material for electric and electronic equipments andoptical equipments.

Next, the aromatic polycarbonate resin of the present invention can beproduced by a process in which the specific2,2-bis(4-hydroxyphenyl)adamantane compound represented by Formula [I-4]described above and the divalent phenols represented by Formula [I-5]described above are reacted with a carbonic ester-forming compound. Inthis case, the aromatic polycarbonate resin can be produced bypolymerization by a method in which interfacial polymerization iscarried out in the presence of a polymerizing solvent, an acid acceptor,an end terminating agent and a catalyst or a method in whichtransesterification is carried out under reduced pressure.

In the above Formula [I-4], the halogen atom, the alkyl group, thealkoxy group, the aryl group, the aryl-substituted alkenyl group and thefluoroalkyl group each represented by R¹ and R² include the same ones asthe atoms and the groups each represented by R¹ and R² in Formula [I-1]described above. Further, an alkyl group having 1 to 6 carbon atoms ismore suitably used as R¹ and R² in this Formula [I-4].

The 2,2-bis(4-hydroxyphenyl)adamantane compound represented by the aboveFormula [1-4] includes, for example, 2,2-bis(4-hydroxyphenyl)adamantane,2,2-bis(3-methyl-4-hydroxyphenyl)adamantane,2,2-bis(3-ethyl-4-hydroxyphenyl)adamantane,2,2-bis(3-n-propyl-4-hydroxyphenyl)adamantane,2,2-bis(3-1-propyl-4-hydroxyphenyl)adamantane,2,2-bis(3-n-butyl-4-hydroxyphenyl)adamantane,2,2-bis(3-1-butyl-4-hydroxyphenyl)adamantane,2,2-bis(3-sec-butyl-4-hydroxyphenyl)adamantane,2,2-bis(3-tert-butyl-4-hydroxyphenyl)adamantane,2,2-bis(3-cyclohexyl-4-hydroxyphenyl)adamantane,2,2-bis(3-phenyl-4-hydroxyphenyl)adamantane,2,2-bis(3-chloro-4-hydroxyphenyl)adamantane,2,2-bis(3-bromo-4-hydroxyphenyl)adamantane,2,2-bis(3,5-dimethyl-4-hydroxyphenyl)adamantane,2,2-bis(3,5-diethyl-4-hydroxyphenyl)adamantane,2,2-bis(3,5-dichloro-4-hydroxyphenyl)adamantane and2,2-bis(3,5-dibromo-4-hydroxyphenyl)adamantane.

The specific examples of the halogen atom and the alkyl grouprepresented by X and R³ in Formula [I-5] include the same ones as theatoms and the groups represented by X and R³ in Formula [I-2] describedabove. The divalent phenols represented by the above Formula [I-5]include 4,4′-dihydroxybiphenyls such as 4,4′-dihydroxybiphenyl,3,3′-difluoro-4,4′-dihydroxybiphenyl,3,3′-dichloro-4,4′-dihydroxybiphenyl,3,3′-dimethyl-4,4′-dihydroxybiphenyl,3,3′-diphenyl-4,4′-dihydroxybipphenyl,3,3′-dicyclohexyl-4,4′-dihydroxybiphenyl,2,2′-dimethyl-4,4′-dihydroxybiphenyl and3,3′,5,5′-tetramethyl-4,4′-dihydroxybiphenyl; bis(hydroxyphenyl)alkanessuch as bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)dipenylmethane,bis(4-hydroxyphenyl)phenylmethane, bis(3-nonyl-4-hydroxyphenyl)methane,bis(3,5-dimethyl-4-hydroxyphenyl)methane,bis(3,5-dibromo-4-hydroxyphenyl)methane,bis(3-chloro-4-hydroxyphenyl)methane,bis(3-fluoro-4-hydroxyphenyl)methane,bis(2-tert-butyl-4-hydroxyphenyl)phenylmethane,bis(2-hydroxyphenyl)methane,bis(2-hydroxyphenyl-4-hydroxyphenyl)methane,bis(2-hydroxy-4-methylphenyl)methane,bis(2-hydroxy-4-methyl-6-tert-butylphenyl)methane,bis(2-hydroxy-4,6-dimethylphenyl)methane,1,1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenyl)ethane,1,1-bis(4-hydroxyphenyl)-1-phenylethane,1,1-bis(4-hydroxy-3-methylphenyl)-1-phenylethane,1,1-bis(4-hydroxy-3-phenylphenyl)-1-phenylethane,2-(4-hydroxy-3-methylphenyl)-2-(4-hydroxyphenyl)-1-phenylethane,1,1-bis(2-tert-butyl-4-hydroxy-3-methylphenyl)ethane,1-phenyl-1,1-bis(3-fluoro-4-hydroxyphenyl)ethane,1,1-bis(2-hydroxy-4-methylphenyl)ethane,2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)propane,2,2-bis(2-methyl-4-hydroxyphenyl)propane,2,2-bis(3-methyl-4-hydroxyphenyl)propane,2,2-bis(3-isopropyl-4-hydroxyphenyl)propane,2,2-bis(3-sec-butyl-4-hydroxyphenyl)propane,2,2-bis(3-phenyl-4-hydroxyphenyl)propane,2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane,2,2-bis(3-chloro-4-hydroxyphenyl)propane,2,2-bis(3-fluoro-4-hydroxyphenyl)propane,2,2-bis(3-bromo-4-hydroxyphenyl)propane,2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane,1,1-bis(2-tert-butyl-4-hydroxy-5-methylphenyl)propane,2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane,2,2-bis(4-hydroxy-3,5-difluorophenyl)propane,2,2-bis(4-hydroxy-3,5-dibromophenyl)propane,2,2-bis(3-bromo-4-hydroxy-5-chlorophenyl)propane,2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane,2,2-bis(2-hydroxy-4-sec-butylphenyl)propane,2,2-bis(2-hydroxy-4,6-dimethylphenyl)propane,2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(3-methyl-4-hydroxyphenyl)butane,1,1-bis(4-hydroxyphenyl)-2-methylpropane,1,1-bis(2-tert-butyl-4-hydroxy-5-methylphenyl)-2-methylpropane,1,1-bis(2-butyl-4-hydroxy-5-methylphenyl)butane,1,1-bis(2-tert-butyl-4-hydroxy-5-methylphenyl)butane,1,1-bis(2-methyl-4-hydroxy-5-tert-pentylphenyl)butane,2,2-bis(4-hydroxy-3,5-dichlorophenyl)butane,2,2-bis(4-hydroxy-3,5-dibromophenyl)butane,2,2-bis(4-hydroxyphenyl)-3-methylbutane,1,1-bis(4-hydroxyphenyl)-3-methylbutane,3,3-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)hexane,2,2-bis(4-hydroxyphenyl)heptane,2,2-bis(2-tert-butyl-4-hydroxy-5-methylphenyl)heptane,2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(4-hydroxyphenyl)nonane,2,2-bis(4-hydroxyphenyl)decane, 1,1-bis(4-hydroxyphenyl)cyclopentane,1,1-bis(4-hydroxyphenyl)cyclohexane,1,1-bis(3-methyl-4-hydroxyphenyl)cyclohexane,1,1-bis(4-hydroxy-3,5-dimethylphenyl)cyclohexane,1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane,1,1-bis(3-phenyl-4-hydroxyphenyl)cyclohexane,1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and1,1-bis(3-methyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane;bis(4-hydroxyphenyl) ethers such as bis(4-hydroxyphenyl) ether andbis(3-fluoro-4-hydroxyphenyl) ether; bis(4-hydroxyphenyl) sulfides; suchas bis(4-hydroxyphenyl) sulfide and bis(3-methyl-4-hydroxyphenyl)sulfide; bis(4-hydroxyphenyl) sulfoxides such as bis(4-hydroxyphenyl)sulfoxide and bis(3-methyl-4-hydroxyphenyl) sulfoxide;bis(4-hydroxyphenyl)sulfones such as bis(4-hydroxyphenyl)sulfone,bis(3-methyl-4-hydroxyphenyl)sulfone andbis(3-phenyl-4-hydroxyphenyl)sulfone; bis(4-hydroxyphenyl) ketones suchas 4,4′-dihydroxybenzophenone; bis(hydroxyphenyl)fluorenes such as9,9-bis(4-hydroxyphenyl)fluorene,9,9-bis(3-methyl-4-hydroxyphenyl)fluorene and9,9-bis(3-phenyl-4-hydroxyphenyl)fluorene; dihydroxy-p-terphenyls suchas 4,4″-dihydroxy-p-terphenyl; dihydroxy-p-quarterphenyls such as4,4′″-dihydroxy-p-quarterphenyl; bis(hydroxyphenyl)pyrazines such as2,5-bis(4-hydroxyphenyl)pyrazine,2,5-bis(4-hydroxyphenyl)-3,6-dimethylpyrazine and2,5-bis(4-hydroxyphenyl)-2,6-diethylpyrazine;bis(hydroxyphenyl)menthanes such as 1,8-bis(4-hydroxyphenyl)menthane,2,8-bis(4-hydroxyphenyl)menthane,1,8-bis(3-methyl-4-hydroxyphenyl)menthane and1,8-bis(4-hydroxy-3,5-dimethylphenyl)menthane; andbis[2-(4-hydroxyphenyl)-2-propyl]benzenes such as1,4-bis[2-(4-hydroxyphenyl)-2-propyl]benzene and1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene.

Among the above various divalent phenols, the phenols represented byFormula [I-6] are preferred, and more suitably used are the phenols inwhich the divalent group represented by X in the above Formulas [I-5]and [I-6] is —C(R⁴R⁵)— (provided that R⁴ and R⁵ each representindependently a hydrogen atom, an alkyl group having 1 to 6 carbonatoms, a phenyl group or a trifluoromethyl group), a substituted ornon-substituted cycloalkylidene group having 6 to 12 carbon atoms or a9,9′-fluorenylidene group. The divalent phenols having such chemicalstructure include, for example, 2,2-bis(4-hydroxyphenyl)propane,2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane,1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane,9,9-bis(4-hydroxyphenyl)fluorene and9,9-bis(3-methyl-4-hydroxyphenyl)fluorene.

Various dihalogenated carbonyls such as phosgene, haloformates such aschloroformate and carbonic ester compounds can be used as the carbonicester-forming compound described above. When using the gaseous carbonicester-forming compound such as phosgene, a method for blowing it into areaction system can suitably be employed. A use proportion of the abovecarbonic ester-forming compound is advisably controlled so that itcorresponds to a stoichiometric ratio (equivalent) in this reaction.

Solvents used for producing conventional aromatic polycarbonate resinsare used for a solvent used in the above reaction. The suited solventsinclude, for example, aromatic hydrocarbon base solvents such as tolueneand xylene, halogenated hydrocarbons such as methylene chloride,chloroform, 1,1-dichloroethane, 1,2-dichloroethane,1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane,1,1,2,2-tetrachloroethane, pentachloroethane and chlorobenzene andacetophenone. The above solvents may be used alone or in combination oftwo or more kinds thereof. Further, two kinds of the solvents which arenot miscible with each other may be used.

Further, capable of being used as the acid acceptor are metal hydroxidessuch as sodium hydroxide, potassium hydroxide, lithium hydroxide andcesium hydroxide, alkaline metal carbonates such as sodium carbonate andpotassium carbonate, organic acids such as pyridine or mixtures thereof.In respect to a use proportion of these acid acceptors, considering astoichiometric ratio (equivalent) in this reaction, one equivalent ofthe acid acceptor per mole of a hydroxyl group of the divalent phenol ofthe raw material or a little excess amount over it, preferably 1 to 5equivalent is advisably used.

Further, monovalent phenols can be used as the end terminating agent.Suitably used are, for example, p-tert-butylphenol, p-phenylphenol,p-cumylphenol, p-perfluorononylphenol, p-(perfluorononylphenyl)phenol,p-tert-perfluorobutylphenol and 1-(p-hydroxybenzyl)perfluorodecane.

Tertiary amines such as triethylamine and quaternary ammonium salts aresuitably used as the catalyst. Further, a method in which a small amountof an antioxidant such as sodium sulfite and hydrosulfite is added tocarry out the reaction may be adopted in this reaction system.

Next, in respect to the reaction conditions in the case of interfacialpolymerization, the reaction temperature is usually 0 to 150° C.,preferably 5 to 40° C., and the reaction pressure may be any of reducedpressure, atmospheric pressure and applied pressure, but the reaction iscarried out preferably at atmospheric pressure or under applied pressureof a self pressure level in the reaction system. The reaction time is,though depending on the reaction temperature, 0.5 minute to 10 hours,preferably one minute to about 2 hours. This reaction may be carried outby any reaction system of a continuous method, a semi-continuous methodand a batch method.

When the reaction is carried out by transesterification, the reaction iscarried out at 120 to 350° C. under reduced pressure. In this case, thedegree of reduced pressure is strengthened in stages as the reactiongoes on, and the pressure is finally reduced to 1 torr or lower to drawout resulting phenols to the outside of the reaction system. Thereaction time is advisably controlled to 1 to 4 hours, and the catalystand the antioxidant may be added if necessary.

The aromatic polycarbonate resin thus obtained can be molded andprocessed by the same methods as in thermoplastic resins such as anaromatic polycarbonate resin using publicly known bisphenol A as a rawmaterial. Further, various additives used in molding and processing, forexample, a heat stabilizer, an antioxidant, a light stabilizer, acolorant, an anti-static agent, a lubricant and a mold releasing agentcan be blended in suited amounts. The aromatic polycarbonate resin thusobtained is excellent in a transparency, a heat resistance and amechanical strength, and therefore it is highly useful as a moldingmaterial for electric and electronic equipments and optical equipments,for example, lenses such as a head lump lens, a prism, an optical fiber,an optical disc and a panel for display equipments.

Next, the present invention shall more specifically be explained withreference to examples and comparative examples.

EXAMPLE I-1

Methylene chloride 700 ml which was a solvent was added to a solutionprepared by dissolving 45 g of 2,2-bis(4-hydroxyphenyl)adamantane and 25g of 1,1-bis(4-hydroxyphenyl)cyclohexane in 1,360 ml of a potassiumhydroxide aqueous solution having a concentration of 2 normal, andphosgene gas was blown into the above solution for 30 minutes in aproportion of 950 ml/minute under cooling while stirring. Then, thisreaction liquid was left standing still and separating, and a methylenechloride solution of an oligomer having a polymerization degree of 2 to5 and having a chloroformate group at a molecular end was obtained inthe organic layer.

Methylene chloride was added to 110 ml of the methylene chloridesolution thus obtained to control the whole amount to 150 ml, and then asolution prepared by dissolving 5 g of1,1-bis(4-hydroxyphenyl)cyclohexane in 50 ml of a potassium hydroxideaqueous solution having a concentration of 2 normal was added thereto.Further, 0.2 g of p-tert-butylphenol was added thereto as a molecularweight-controlling agent. Then, 1.0 ml of a triethylamine aqueoussolution having a concentration of 7% was added as a catalyst whilevigorously stirring the above mixed solution to carry out reaction at25° C. for 1.5 hour under stirring.

After finishing the reaction, the reaction product thus obtained wasdiluted with one liter of methylene chloride and washed twice with 1.5liter of water. Then, it was washed with hydrochloric acid having aconcentration of 0.05 normal and then further washed twice with oneliter of water. The organic layer thus obtained was thrown into methanolto carry out refining by reprecipitation, whereby a powder of anaromatic polycarbonate resin was obtained.

A solution of the aromatic polycarbonate resin obtained above having aconcentration of 0.5 g/liter using methylene chloride as a solvent had areduced viscosity (η_(sp)/c) of 0.6 deciliter/g at 20° C. Further,confirmation of the structure of the above aromatic polycarbonate resinby ¹H-NMR spectrum analysis resulted in finding that the chemicalstructure thereof comprised the following repetitive unit:

Further, a glass transition temperature of the above aromaticpolycarbonate resin was measured to find that it was 238° C. and confirmthat it had a very high heat resistance. Further, a methylene chloridesolution of the above aromatic polycarbonate resin was used to produce afilm by casting to find that it was colorless and highly transparent.

EXAMPLE I-2

Methylene chloride 700 ml which was a solvent was added to a solutionprepared by dissolving 75 g of 2,2-bis(4-hydroxyphenyl)adamantane in1,360 ml of a potassium hydroxide aqueous solution having aconcentration of 2 normal, and phosgene gas was blown into the abovesolution for 30 minutes in a proportion of 950 ml/minute under coolingwhile stirring. Then, this reaction liquid was left standing still andseparating, and a methylene chloride solution of an oligomer having apolymerization degree of 2 to 5 and having a chloroformate group at amolecular end was obtained in the organic layer.

Methylene chloride was added to 110 ml of the methylene chloridesolution thus obtained to control the whole amount to 150 ml, and then asolution prepared by dissolving 6 g of9,9-bis(3-methyl-4-hydroxyphenyl)fluorene in 50 ml of a potassiumhydroxide aqueous solution having a concentration of 2 normal was addedthereto. Further, 0.2 g of p-tert-butylphenol was added thereto as amolecular weight-controlling agent. Then, 1.4 ml of a triethylamineaqueous solution having a concentration of 7% was added as a catalystwhile vigorously stirring the above mixed solution to carry out reactionat 25° C. for 1.5 hour under stirring.

After finishing the reaction, the reaction product thus obtained wasdiluted with 0.5 liter of methylene chloride and washed twice with 0.5liter of water. Then, it was washed with hydrochloric acid having aconcentration of 0.01 normal and then further washed twice with 0.5liter of water. The organic layer thus obtained was thrown into methanolto carry out refining by reprecipitation, whereby a powder of anaromatic polycarbonate resin was obtained.

A solution of the aromatic polycarbonate resin obtained above having aconcentration of 0.5 g/liter using methylene chloride as a solvent had areduced viscosity (η_(sp)/c) of 0.5 deciliter/g at 20° C. Further,confirmation of the structure of the above aromatic polycarbonate resinby ¹H-NMR spectrum analysis resulted in finding that the chemicalstructure thereof comprised the following repetitive unit:

Further, a glass transition temperature of the above aromaticpolycarbonate resin was measured to find that it was 282° C. and confirmthat it had a very high heat resistance. Further, a methylene chloridesolution of the above aromatic polycarbonate resin was used to produce afilm by casting to find that it was colorless and highly transparent.

EXAMPLE I-3

Methylene chloride 900 ml which was a solvent was added to a solutionprepared by dissolving 170 g of 1,1-bis(4-hydroxyphenyl)cyclohexane in1,530 ml of a potassium hydroxide aqueous solution having aconcentration of 2 normal, and phosgene gas was blown into the abovesolution for 30 minutes in a proportion of 950 ml/minute under coolingwhile stirring. Then, this reaction liquid was left standing still andseparating, and a methylene chloride solution of an oligomer having apolymerization degree of 2 to 5 and having a chloroformate group at amolecular end was obtained in the organic layer.

Methylene chloride was added to 110 ml of the methylene chloridesolution thus obtained to control the whole amount to 150 ml, and then asolution prepared by dissolving 6 g of2,2-bis(3,5-dimethyl-4-hydroxyphenyl)adamantane in 50 ml of a potassiumhydroxide aqueous solution having a concentration of 2 normal was addedthereto. Further, 0.2 g of p-tert-butylphenol was added thereto as amolecular weight-controlling agent. Then, 1.0 ml of a triethylamineaqueous solution having a concentration of 7% was added as a catalystwhile vigorously stirring the above mixed solution to carry out reactionat 25° C. for 1.5 hour under stirring.

After finishing the reaction, the reaction product thus obtained wasdiluted with 0.5 liter of methylene chloride and washed twice with 0.5liter of water. Then, it was washed with hydrochloric acid having aconcentration of 0.01 normal and then further washed twice with 0.5liter of water. The organic layer thus obtained was thrown into methanolto carry out refining by reprecipitation, whereby a powder of anaromatic polycarbonate resin was obtained.

A solution of the aromatic polycarbonate resin obtained above having aconcentration of 0.5 g/liter using methylene chloride as a solvent had areduced viscosity (η_(sp)/c) of 0.4 deciliter/g at 20° C. Further,confirmation of the structure of the above aromatic polycarbonate resinby ¹H-NMR spectrum analysis resulted in finding that the chemicalstructure thereof comprised the following repetitive unit:

Further, a glass transition temperature of the above aromaticpolycarbonate resin was measured to find that it was 207° C. and confirmthat it had a very high heat resistance. Further, a methylene chloridesolution of the above aromatic polycarbonate resin was used to produce afilm by casting to find that it was colorless and highly transparent.

COMPARATIVE EXAMPLE I-1

The same procedure as in Example I-2 was repeated, except that inExample I-2, 5 g of 2,2-bis(4-hydroxyphenyl)adamantane was added inplace of 6 g of 9,9-bis(3-methyl-4-hydroxyphenyl)fluorene added at thelatter stage.

A solution of the aromatic polycarbonate resin obtained above having aconcentration of 0.5 g/liter using methylene chloride as a solvent had areduced viscosity (η_(sp)/c) of 0.5 deciliter/g at 20° C. Further,confirmation of the structure of the above aromatic polycarbonate resinby ¹H-NMR spectrum analysis resulted in finding that the chemicalstructure thereof comprised the following repetitive unit:

Further, a glass transition temperature of the above aromaticpolycarbonate resin was measured to find that it was 298° C. and confirmthat it had a very high heat resistance. However, a film produced bycasting using a methylene chloride solution of the above aromaticpolycarbonate resin was whitened due to crystallization and, so that ithad a low transparency.

II. Second Invention

The aromatic polycarbonate resin of the present invention is an aromaticpolycarbonate resin which comprises the repetitive unit represented byFormula [II-1] described above and in which the solution having aconcentration of 0.5 g/deciliter using methylene chloride as a solventhas a reduced viscosity (η_(sp)/c) of 0.1 deciliter/g or more which ismeasured at 20° C.

In the above aromatic polycarbonate resin, the halogen atom representedby R¹ in Formula [II-1] described above includes a fluorine atom, achlorine atom, a bromine atom and an iodine atom. The alkyl group having1 to 6 carbon atoms represented by R¹ in the above formula includesmethyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl,tert-butyl, n-pentyl, n-hexyl, cyclopentyl and cyclohexyl. The alkoxygroup having 1 to 6 carbon atoms includes methoxy, ethoxy, n-propoxy,i-propoxy, i-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy andn-hexyloxy. The aryl group having 6 to 12 carbon atoms includes phenyl,biphenyl, triphenyl and naphthyl, and the aryl-substituted alkenyl grouphaving 7 to 13 carbon atoms includes benzyl, phenethyl, styryl andcinnamyl. Further, the fluoroalkyl group having 1 to 6 carbon atomsincludes monofluoromethyl, difluoromethyl and trifluoromethyl. Further,the resin in which m in Formula [II-1] described above is 1 to 4 can beused, and the resin in which m 1 to 2 is more preferred. When m is 2 ormore, respective R¹ may be the same of different.

The aromatic polycarbonate resin of the resin present invention in whichR¹ in Formula [II-1] described above is an alkyl group having 1 to 6carbon atoms is particularly preferred since it is excellent in a heatresistance.

Also, the aromatic polycarbonate resin of a copolymer type according tothe present invention is an aromatic polycarbonate resin which comprisesthe repetitive unit (II-1) represented by Formula [II-2] described aboveand the repetitive unit (II-2) represented by Formula [II-3] describedabove and in which the solution having a concentration of 0.5g/deciliter using methylene chloride as a solvent has a reducedviscosity (η_(sp)/c) of 0.1 deciliter/g or more which is measured at 20°C.

In the above aromatic polycarbonate resin, the halogen atom, the alkylgroup, the alkoxy group, the aryl group, the aryl-substituted alkenylgroup and the fluoroalkyl group each represented by R² in Formula [II-2]include the same ones as those each represented by R¹ in Formula [I-1]described above. Also, the resin in which n in Formula [II-2] describedabove is 1 to 4 is used, and the resin in which n 1 to 2 is morepreferred. Further, the aromatic polycarbonate resin comprising therepetitive unit (II-1) in which R² in Formula [II-2] described above isan alkyl group having 1 to 6 carbon atoms is preferred since it isexcellent in a heat resistance.

Also, the halogen atom represented by R³ in Formula [II-3] includes afluorine atom, a chlorine atom, a bromine atom and an iodine atom. Thealkyl group having 1 to 12 carbon atoms includes methyl, ethyl,n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, n-pentyl,n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl,cyclopentyl and cyclohexyl. The alkoxy group having 1 to 12 carbon atomsincludes methoxy, ethoxy, n-propoxy, i-propoxy, i-butoxy, sec-butoxy,tert-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy,n-nonyloxy, n-decyloxy, n-undecyloxy and n-dodecyloxy. The aryl grouphaving 6 to 12 carbon atoms includes phenyl, biphenyl, triphenyl andnaphthyl, and the aryl-substituted alkenyl group having 7 to 13 carbonatoms includes benzyl, phenethyl, styryl and cinnamyl. Further, thefluoroalkyl group having 1 to 12 carbon atoms includes monofluoromethyl,difluoromethyl and trifluoromethyl. Among the above varioussubstituents, the preferred ones include methyl, ethyl, methoxy, ethoxy,phenyl and trifluoromethyl. Further, p in Formula [II-3] may be 0, thatis, it may be only a hydrogen atom or may have any of 1 to 4substituents.

Given are the resins in which X in the above Formula [II-3] is a singlebond, —O—, —CO—, —S—, —SO—, —SO₂—, —C(R⁴R⁵)— (provided that R⁴ and R⁵each represent independently a hydrogen atom, an alkyl group having 1 to6 carbon atoms, a phenyl group or a trifluoromethyl group), asubstituted or non-substituted cycloalkylidene group having 6 to 12carbon atoms, a 9,9′-fluorenylidene group, a 1,8-menthanediyl group, a2,8-menthanediyl group, a substituted or non-substituted pyrazylidenegroup, a substituted or non-substituted arylene group having 6 to 12carbon atoms or —C(CH₃)₂-ph-C(CH₃)₂— (provided that ph represents aphenylene group). Among them, the resins in which X is—C(R⁴R⁵)-(provided that R⁴ and R⁵ each represent independently ahydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl groupor a trifluoromethyl group), a substituted or non-substitutedcycloalkylidene group having 6 to 12 carbon atoms or a9,9′-fluorenylidene group are preferred since they are excellent in aheat resistance.

In this regard, the alkyl group having 1 to 6 carbon atoms representedby R⁴ and R⁵ described above in —C(R⁴R⁵)— represented by X includes thesame ones as the alkyl groups having 1 to 6 carbon atoms represented byR¹ described above. Also, the substituted or non-substitutedcycloalkylidene group having 6 to 12 carbon atoms represented by Xincludes cyclopentylidene, cyclohexylidene,3,3,5-trimethylcyclohexylidene, cycloheptylidene and cyclooctylidene,and the substituted or non-substituted arylene group having 6 to 12carbon atoms includes phenylene, biphenylene,1,4-phenylenebis(1-methylethylidene) and1,3-phenylenebis(1-methylethylidene).

Further, the above repetitive unit (II-2) constituting the aromaticpolycarbonate resin has preferably a structure containing a p-phenylenegroup represented by Formula [II-4] since the resin is excellent in aheat resistance and a mechanical strength.

Next, a content proportion of the repetitive unit (II-1) to therepetitive unit (II-2) each constituting the above aromaticpolycarbonate resin of a copolymer type shall not specifically berestricted, and a content proportion [(II-1)/((II-1)+(II-2))] of therepetitive unit (II-1) to the whole repetitive units falls preferably ina range of 0.05 to 0.99 in terms of a mole ratio. This is because of thereasons that if a mole ratio of the above repetitive unit (II-1) islower than 0.05, the moldability is good but the degree of a rise in theheat resistance is small and that if the above mole ratio is higher than0.99, the excellent heat resistance is shown but the solubility in asolvent is low and the moldability is reduced. Further, the abovecontent proportion of the repetitive unit (II-1) to the whole repetitiveunits falls preferably in a range of 0.05 to 0.95 because it provides agood balance of the heat resistance and the mechanical strength with themolding processability.

In the aromatic polycarbonate resin of the present invention, thesolution having a concentration of 0.5 g/deciliter using methylenechloride as a solvent has a reduced viscosity (η_(sp)/c) of 0.1deciliter/g or more which is measured at 20° C. This is because if theabove reduced viscosity is less than 0.1 deciliter/g, the aromaticpolycarbonate resin can not sufficiently obtain a heat resistance and amechanical strength. The resin in which the above reduced viscosity is0.3 to 3.0 deciliter/g is particularly suited as a molding material forelectric and electronic equipments and optical equipments.

Next, the aromatic polycarbonate resin of the present invention can beproduced by a process in which the 1,3-bis(4-hydroxyphenyl)adamantanecompound represented by Formula [II-5] described above is reacted with acarbonic ester-forming compound. Further, the aromatic polycarbonateresin of a copolymer type can be produced by a process in which the1,3-bis(4-hydroxyphenyl)adamantane compound represented by Formula[II-6] described above and the divalent phenols represented by Formula[II-7] described above are reacted with a carbonic ester-formingcompound. In carrying out these reactions, the aromatic polycarbonateresin can be produced by a method in which interfacial polymerization iscarried out in the presence of a polymerizing solvent, an acid acceptor,an end terminating agent and a catalyst or a method in whichtransesterification is carried out under reduced pressure.

In Formulas [II-5] and [II-6], the halogen atom, the alkyl group, thealkoxy group, the aryl group, the aryl-substituted alkenyl group and thefluoroalkyl group each represented by R¹ to R⁶ include the same ones asthe atoms and the groups each represented by R¹ in Formula [II-1]described above. In this regard, the 1,3-bis(4-hydroxyphenyl)adamantanecompound represented by the above Formulas [II-5] and [II-6] includes,for example, 1,3-bis(3-chloro-4-hydroxyphenyl)adamantane,1,3-bis(3-bromo-4-hydroxyphenyl)adamantane,1,3-bis(3-fluoro-4-hydroxyphenyl)adamantane,1,3-bis(3-methyl-4-hydroxyphenyl)adamantane,1,3-bis(3-ethyl-4-hydroxyphenyl)adamantane,1,3-bis(3-n-propyl-4-hydroxyphenyl)adamantane,1,3-bis(3-1-propyl-4-hydroxyphenyl)adamantane,1,3-bis(3-n-butyl-4-hydroxyphenyl)adamantane,1,3-bis(3-1-butyl-4-hydroxyphenyl)adamantane,1,3-bis(3-sec-butyl-4-hydroxyphenyl)adamantane,1,3-bis(3-tert-butyl-4-hydroxyphenyl)adamantane,1,3-bis(3-n-pentyl-4-hydroxyphenyl)adamantane,1,3-bis(3-n-hexyl-4-hydroxyphenyl)adamantane,1,3-bis(3-cyclohexyl-4-hydroxyphenyl)adamantane,1,3-bis(3-methoxy-4-hydroxyphenyl)adamantane,1,3-bis(3-ethoxy-4-hydroxyphenyl)adamantane,1,3-bis(3-phenyl-4-hydroxyphenyl)adamantane,1,3-bis(3-benzyl-4-hydroxyphenyl)adamantane,1,3-bis(3-naphthyl-4-hydroxyphenyl)adamantane,1,3-bis(3-tetrafluormethyl-4-hydroxyphenyl)adamantane,1,3-bis(3,5-dichloro-4-hydroxyphenyl)adamantane,1,3-bis(3,5-dibromo-4-hydroxyphenyl)adamantane,1,3-bis(3,5-difluoro-4-hydroxyphenyl)adamantane,1,3-bis(3,5-dimethyl-4-hydroxyphenyl)adamantane,1,3-bis(3,5-diethyl-4-hydroxyphenyl)adamantane,1,3-bis(3,5-dimethoxy-4-hydroxyphenyl)adamantane and1,3-bis(3,5-diethoxy-4-hydroxyphenyl)adamantane.

The halogen atom, the alkyl group, the alkoxy group, the aryl group, thearyl-substituted alkenyl group and the fluoroalkyl group eachrepresented by X and R³ in Formula [II-7] described above include thesame ones as the atoms and the groups each represented by X and R³ inFormula [II-3] described above. The compounds given as the examples ofthe divalent phenols represented by Formula [1-5] in the first inventionapply to the above divalent phenols represented by Formula [II-7].

The phenol represented by Formula [II-8] described above is suitablyused as the divalent phenol used for producing the aromaticpolycarbonate resin of the present invention. Further, the divalentphenol in which X in Formulas [II-7] and [II-8] described above is—C(R⁴R⁵)— (provided that R⁴ and R⁵ each represent independently ahydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl groupor a trifluoromethyl group), a substituted or non-substitutedcycloalkylidene group having 6 to 12 carbon atoms or a9,9′-fluorenylidene group is preferably used since the aromaticpolycarbonate resin which is excellent in a heat resistance and amechanical strength is obtained. The suitable divalent phenols havingsuch chemical structure include, for example,2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane,1,1-bis(4-hydroxyphenyl)cyclohexane,1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane,9,9-bis(4-hydroxyphenyl)fluorene and9,9-bis(3-methyl-4-hydroxyphenyl)fluorene.

Also, the compounds given in the first invention apply to the carbonicester-forming compound described above. When using the gaseous carbonicester-forming compound such as phosgene, a method for blowing it into areaction system can suitably be adopted.

Solvents used for producing conventional aromatic polycarbonate resinsare used for a solvent used in the above reaction, and the solventsgiven in the first invention apply thereto. The above solvents may beused alone or in combination of two or more kinds thereof. Further, twokinds of the solvents which are not miscible with each other may beused.

Also, those described in the first invention apply as they are to theacid acceptor, the end terminating agent and the catalyst.

Further, those described in the first invention also apply as they areto the reaction conditions in the case of interfacial polymerization orthe reaction conditions in the case of transesterification.

Those described in the first invention also apply as they are to moldingand processing of the aromatic polycarbonate resin thus obtained andvarious additives used therein.

The aromatic polycarbonate resin thus obtained is excellent in atransparency, a heat resistance and a mechanical strength, and thereforeit is highly useful as a molding material for electric and electronicequipments and optical equipments, for example, lenses such as a headlump lens, a prism, an optical fiber, an optical disc and a panel fordisplay equipments.

Next, the present invention shall more specifically be explained withreference to examples and comparative examples.

EXAMPLE II-1

Methylene chloride 900 ml which was a solvent was added to a solutionprepared by dissolving 170 g of 1,1-bis(4-hydroxyphenyl)cyclohexane in1,530 ml of a potassium hydroxide aqueous solution having aconcentration of 2 normal, and phosgene gas was blown into the abovesolution for 30 minutes in a proportion of 950 ml/minute under coolingwhile stirring. Then, this reaction liquid was left standing still andseparating, and a methylene chloride solution of an oligomer having apolymerization degree of 2 to 5 and having a chloroformate group at amolecular end was obtained in the organic layer.

Methylene chloride was added to 110 ml of the methylene chloridesolution thus obtained to control the whole amount to 150 ml, and then asolution prepared by dissolving 5.5 g of1,3-bis(4-hydroxyphenyl)adamantane in 50 ml of a potassium hydroxideaqueous solution having a concentration of 2 normal was added thereto.Further, 0.2 g of p-tert-butylphenol was added thereto as a molecularweight-controlling agent. Then, 1.0 ml of a triethylamine aqueoussolution having a concentration of 7% was added as a catalyst whilevigorously stirring the above mixed solution to carry out reaction at25° C. for 1.5 hour under stirring.

After finishing the reaction, the reaction product thus obtained wasdiluted with 0.5 liter of methylene chloride and washed twice with 0.5liter of water. Then, it was washed with 0.5 liter of hydrochloric acidhaving a concentration of 0.01 normal and then further washed twice with0.5 liter of water. The organic layer thus obtained was thrown intomethanol to carry out refining by reprecipitation, whereby an aromaticpolycarbonate resin was obtained.

A solution of the aromatic polycarbonate resin obtained above having aconcentration of 0.5 g/deciliter using methylene chloride as a solventhad a reduced viscosity (η_(sp)/c) of 0.4 deciliter/g at 20° C. Further,confirmation of the structure of the above aromatic polycarbonate resinby ¹H-NMR spectrum analysis resulted in finding that the chemicalstructure thereof comprised the following repetitive unit:

Further, a glass transition temperature of the above aromaticpolycarbonate resin was measured to find that it was 189° C. and confirmthat it had a very high heat resistance. Further, a methylene chloridesolution of the above aromatic polycarbonate resin was used to produce afilm by casting to find that it was colorless and highly transparent.

EXAMPLE II-2

The same procedure as in Example II-1 was repeated, except that 6 g of1,3-bis(3,5-dimethyl-4-hydroxyphenyl)adamantane was added in place of1,3-bis(4-hydroxyphenyl)adamantane which was the raw material used inExample II-1.

A solution of the aromatic polycarbonate resin obtained above having aconcentration of 0.5 g/deciliter using methylene chloride as a solventhad a reduced viscosity (η_(sp)/c) of 0.5 deciliter/g at 20° C. Further,confirmation of the structure of the above aromatic polycarbonate resinby ¹H-NMR spectrum analysis resulted in finding that the chemicalstructure thereof comprised the following repetitive unit:

Further, a glass transition temperature of the above aromaticpolycarbonate resin was measured to find that it was 196° C. and confirmthat it had a very high heat resistance. Further, a methylene chloridesolution of the above aromatic polycarbonate resin was used to produce afilm by casting to find that it was colorless and highly transparent.

EXAMPLE II-3

Methylene chloride 900 ml which was a solvent was added to a solutionprepared by dissolving 170 g of 2,2-bis(4-hydroxyphenyl)propane in 1,530ml of a potassium hydroxide aqueous solution having a concentration of 2normal, and phosgene gas was blown into the above solution for 30minutes in a proportion of 950 ml/minute under cooling while stirring.Then, this reaction liquid was left standing still and separating, and amethylene chloride solution of an oligomer having a polymerizationdegree of 2 to 5 and having a chloroformate group at a molecular end wasobtained in the organic layer.

Methylene chloride was added to 110 ml of the methylene chloridesolution thus obtained to control the whole amount to 150 ml, and then asolution prepared by dissolving 5.5 g of1,3-bis(3,5-dimethyl-4-hydroxyphenyl)adamantane in 50 ml of a potassiumhydroxide aqueous solution having a concentration of 2 normal was addedthereto. Further, 0.2 g of p-tert-butylphenol was added thereto as amolecular weight-controlling agent. Then, 1.0 ml of a triethylamineaqueous solution having a concentration of 7% was added as a catalystwhile vigorously stirring the above mixed solution to carry out reactionat 25° C. for 1.5 hour under stirring.

After finishing the reaction, the reaction product thus obtained wasdiluted with 0.5 liter of methylene chloride and washed twice with 0.5liter of water. Then, it was washed with 0.5 liter of hydrochloric acidhaving a concentration of 0.01 normal and then further washed twice with0.5 liter of water. The organic layer thus obtained was thrown intomethanol to carry out refining by reprecipitation, whereby an aromaticpolycarbonate resin was obtained.

A solution of the aromatic polycarbonate resin obtained above having aconcentration of 0.5 g/deciliter using methylene chloride as a solventhad a reduced viscosity (η_(sp)/c) of 0.4 deciliter/g at 20° C. Further,confirmation of the structure of the above aromatic polycarbonate resinby ¹H-NMR spectrum analysis resulted in finding that the chemicalstructure thereof comprised the following repetitive unit:

Further, a glass transition temperature of the above aromaticpolycarbonate resin was measured to find that it was 170° C. and confirmthat it had a high heat resistance. Further, a methylene chloridesolution of the above aromatic polycarbonate resin was used to produce afilm by casting to find that it was colorless and highly transparent.

COMPARATIVE EXAMPLE II-1

Only 1,1-bis(4-hydroxyphenyl)cyclohexane was used as the divalent phenolof the raw material to produce an aromatic polycarbonate resin byconventional interfacial polymerization.

A solution of the aromatic polycarbonate resin obtained above having aconcentration of 0.5 g/deciliter using methylene chloride as a solventhad a reduced viscosity (η_(sp)/c) of 0.4 deciliter/g at 20° C. It wasconfirmed that the chemical structure of the above aromaticpolycarbonate resin comprised the following repetitive unit:

Further, a glass transition temperature of the above aromaticpolycarbonate resin was measured to find that it was 170° C.

III. Third Invention

The optical part-molding material of the present invention comprises thearomatic polycarbonate resin which comprises the repetitive unitrepresented by Formula [III-1] or Formula [III-2] described above and inwhich the solution having a concentration of 0.5 g/deciliter usingmethylene chloride as a solvent has a reduced viscosity (η_(sp)/c) of0.1 deciliter/g or more which is measured at 20° C. or the aromaticpolycarbonate resin which comprises the repetitive unit (III-1)represented by Formula [III-3] described above and the repetitive unit(III-2) represented by Formula [III-4] or Formula [III-7] describedabove and in which the solution having a concentration of 0.5g/deciliter using methylene chloride as a solvent has a reducedviscosity (η_(sp)/c) of 0.1 deciliter/g or more which is measured at 20°C.

In the repetitive unit represented by Formula [III-1] or Formula [III-2]which is the structural unit for the above aromatic polycarbonate resin,the halogen atom represented by R¹ and R² includes a fluorine atom, achlorine atom, a bromine atom and an iodine atom. The alkyl group having1 to 6 carbon atoms represented by R¹ and R² includes methyl, ethyl,n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, n-pentyl,n-hexyl, cyclopentyl and cyclohexyl. The alkoxy group having 1 to 6carbon atoms includes methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy,i-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy and n-hexyloxy. The arylgroup having 6 to 12 carbon atoms includes phenyl, biphenyl andnaphthyl, and the aryl-substituted alkenyl group having 7 to 13 carbonatoms includes benzyl, phenethyl, styryl and cinnamyl. Further, thefluoroalkyl group having 1 to 12 carbon atoms includes monofluoromethyl,difluoromethyl and trifluoromethyl. Further, a and b may be 0, that is,it may be only a hydrogen atom or may have 1 to 4, preferably 1 to 2substituents.

Further, the aromatic polycarbonate resin in which R¹ and R² in Formula[III-1] or Formula [III-2] are the alkyl groups having 1 to 6 carbonatoms is preferred as a molding material for optical parts since it isexcellent in an heat resistance. Among the above alkyl groups having 1to 6 carbon atoms, methyl is more preferred.

In Formula [III-1] described above, the halogen atom represented by R³includes the same ones as in R¹ and R² described above. The alkyl grouphaving 1 to 12 carbon atoms represented by R³ includes methyl, ethyl,n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, n-pentyl,n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl,cyclopentyl and cyclohexyl. The alkoxy group having 1 to 12 carbon atomsincludes methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy,sec-butoxy, tert-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy,n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy and n-dodecyloxy. Thearyl group having 6 to 12 carbon atoms includes phenyl, biphenyl andnaphthyl, and the aryl-substituted alkenyl group having 7 to 13 carbonatoms includes benzyl, phenethyl, styryl and cinnamyl. Further, thefluoroalkyl group having 1 to 12 carbon atoms includes monofluoromethyl,difluoromethyl and trifluoromethyl. Among the above varioussubstituents, methyl, ethyl, methoxy, ethoxy, phenyl and trifluoromethylare particularly preferred. Further, c may be 0, that is, it may be onlya hydrogen atom or may have 1 to 14 substituents.

In Formula [III-3], the halogen atom, the alkyl group, the alkoxy group,the aryl group, the aryl-substituted alkenyl group and the fluoroalkylgroup each represented by R⁴, R⁵ and R⁶ include the same ones as theatoms and the groups each represented by R¹, R² and R³ described above.

In Formula [III-4], the halogen atom, the alkyl group, the alkoxy group,the aryl group, the aryl-substituted alkenyl group and the fluoroalkylgroup each represented by R⁷ and R⁸ include the same ones as the atomsand the groups each represented by R³ described above. X in the aboveFormula [III-4] includes a single bond, —O—, —CO—, —S—, —SO—, —SO₂—,—C(R⁹R¹⁰)— (provided that R⁹ and R¹⁰ each represent independently ahydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl groupor a trifluoromethyl group), a substituted or non-substitutedcycloalkylidene group having 6 to 12 carbon atoms, a 9,9′-fluorenylidenegroup, a 1,8-menthanediyl group, a 2,8-menthanediyl group, a substitutedor non-substituted pyrazylidene group, a substituted or non-substitutedarylene group having 6 to 12 carbon atoms, —C(CH₃)₂-ph-C(CH₃)₂—(provided that ph represents a phenylene group) or a substituted ornon-substituted adamantyl group represented by Formula [III-5] orFormula [III-6]. The halogen atom, the alkyl group, the alkoxy group,the aryl group, the aryl-substituted alkenyl group and the fluoroalkylgroup each represented by R¹¹ and R¹² in the above Formula [III-5] andFormula [III-6] include the same ones as the atoms and the groups eachrepresented by R³ described above. Further, i and j may be 0 or it mayhave 1 to 14 substituents.

In this regard, the alkyl group having 1 to 6 carbon atoms representedby R⁹ and R¹⁰ described above includes the ones as in R¹ and R²described above. Further, the substituted or non-substitutedcycloalkylidene group having 6 to 12 carbon atoms represented by Xincludes cyclopentylidene, cyclohexylidene and cyclooctylidene, and thesubstituted or non-substituted arylene group having 6 to 12 carbon atomsincludes phenylene, biphenylene, naphthylene,1,4-phenylenebis(1-methylethylidene) and1,3-phenylenebis(1-methylethylidene). In the above Formula [III-4], gand h may be 0 or it may have 1 to 4 substituents.

Further, the resin in which X in the above Formulas [III-4] is—C(R⁹R¹⁰)— (provided that R⁹ and R¹⁰ each represent independently ahydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl groupor a trifluoromethyl group), a substituted or non-substitutedcycloalkylidene group having 6 to 12 carbon atoms or a9,9′-fluorenylidene group is preferred since it is excellent in anoptical property, a heat resistance and a mechanical strength.

The aromatic polycarbonate resin in which the repetitive unit (III-2)has the structural unit represented by Formula [III-7] is preferredsince it is excellent in a heat resistance and a mechanical strength.

A content proportion of the repetitive unit (III-1) to the repetitiveunit (III-2) each constituting the above aromatic polycarbonate resinshall not specifically be restricted, and a content proportion[(III-1)/((III-1)+(III-2))] of the repetitive unit (III-1) to the wholerepetitive units falls preferably in a range of 0.05 to 0.99 in terms ofa mole ratio. This is because of the reasons that if a mole ratio of theabove repetitive unit (III-1) is lower than 0.05, the moldingprocessability is good but the degree of a rise in the heat resistanceis small in a certain case and that if the above mole ratio is higherthan 0.99, the particularly excellent heat resistance is shown but themolding processability is reduced in a certain case. In the case of theabove aromatic polycarbonate resin of a copolymer type, the contentproportion of the above repetitive unit (III-1) to the whole repetitiveunits falls particularly preferably in a range of 0.05 to 0.95 becauseit provides a good balance of the heat resistance and the mechanicalstrength with the moldability.

The aromatic polycarbonate resin used for the optical part-moldingmaterial of the present invention is a resin in which the solutionhaving a concentration of 0.5 g/deciliter using methylene chloride as asolvent has a reduced viscosity (η_(sp)/c) of 0.1 deciliter/g or morewhich is measured at 20° C. This is because of the reasons that if theabove reduced viscosity is less than 0.1 deciliter/g, the aromaticpolycarbonate resin can not sufficiently obtain a heat resistance and amechanical strength and that characteristics required to the moldingmaterial for optical parts can not sufficiently be satisfied. Thearomatic polycarbonate resin in which a reduced viscosity is 0.3 to 3.0deciliter/g is particularly suited as the molding material for opticalequipment parts.

Next, the aromatic polycarbonate resin used in the present invention canbe produced by a process in which a 2,2-bis(hydroxyphenyl)adamantanecompound alone or the same and the divalent phenols are reacted with acarbonic ester-forming compound. In this case, it can be produced by amethod in which interfacial polymerization is carried out in thepresence of a polymerizing solvent, an acid acceptor, an end terminatingagent and a catalyst or a method in which transesterification is carriedout under reduced pressure.

The adamantane compound used for producing the above aromaticpolycarbonate resin includes, for example,2,2-bis(4-hydroxyphenyl)adamantane, 2,2-bis(3-hydroxyphenyl)adamantane,2,2-bis(3-chloro-4-hydroxyphenyl)adamantane,2,2-bis(3-bromo-4-hydroxyphenyl)adamantane,2,2-bis(3-fluoro-4-hydroxyphenyl)adamantane,2,2-bis(3-methyl-4-hydroxyphenyl)adamantane,2,2-bis(3-ethyl-4-hydroxyphenyl)adamantane,2,2-bis(3-n-propyl-4-hydroxyphenyl)adamantane,2,2-bis(3-1-propyl-4-hydroxyphenyl)adamantane,2,2-bis(3-n-butyl-4-hydroxyphenyl)adamantane,2,2-bis(3-1-butyl-4-hydroxyphenyl)adamantane,2,2-bis(3-sec-butyl-4-hydroxyphenyl)adamantane,2,2-bis(3-tert-butyl-4-hydroxyphenyl)adamantane,2,2-bis(3-n-pentyl-4-hydroxyphenyl)adamantane,2,2-bis(3-n-hexyl-4-hydroxyphenyl)adamantane,2,2-bis(3-cyclohexyl-4-hydroxyphenyl)adamantane,2,2-bis(3-methoxy-4-hydroxyphenyl)adamantane,2,2-bis(3-ethoxy-4-hydroxyphenyl)adamantane,2,2-bis(3-phenyl-4-hydroxyphenyl)adamantane,2,2-bis(3-benzyl-4-hydroxyphenyl)adamantane,2,2-bis(3-naphthyl-4-hydroxyphenyl)adamantane,2,2-bis(3-tetrafluormethyl-4-hydroxyphenyl)adamantane,2,2-bis(3,5-dichloro-4-hydroxyphenyl)adamantane,2,2-bis(3,5-dibromo-4-hydroxyphenyl)adamantane,2,2-bis(3,5-difluoro-4-hydroxyphenyl)adamantane,2,2-bis(3,5-dimethyl-4-hydroxyphenyl)adamantane,2,2-bis(3,5-diethyl-4-hydroxyphenyl)adamantane,2,2-bis(3,5-dimethoxy-4-hydroxyphenyl)adamantane and2,2-bis(3,5-diethoxy-4-hydroxyphenyl)adamantane. The above2,2-bis(hydroxyphenyl)adamantane compounds may be used in combination oftwo or more kinds thereof.

The divalent phenol used for producing the above aromatic polycarbonateresin includes 4,4′-dihydroxybiphenyls; bis(hydroxyphenyl)alkanes;bis(4-hydroxyphenyl) ethers; bis(4-hydroxyphenyl) sulfides;bis(4-hydroxyphenyl) sulfoxides; bis(4-hydroxyphenyl)sulfones;bis(4-hydroxyphenyl) ketones; bis(hydroxyphenyl)fluorenes;dihydroxy-p-terphenyls; dihydroxy-p-quarterphenyls;bis(hydroxyphenyl)pyrazines; bis(hydroxyphenyl)menthanes; andbis[2-(4-hydroxyphenyl)-2-propyl]benzenes, all of which have been givenas the examples in the first invention. Further, it includes1,3-bis(4-hydroxyphenyl)adamantane,1,3-bis(3-chloro-4-hydroxyphenyl)adamantane and1,3-bis(3-methyl-4-hydroxyphenyl)adamantane.

Also, the compounds given in the first invention apply to the carbonicester-forming compound described above. When using the gaseous carbonicester-forming compound such as phosgene, a method for blowing it into areaction system can suitably be adopted.

Solvents used for producing conventional aromatic polycarbonate resinsare used for a solvent used in the above reaction, and the solventsgiven in the first invention apply thereto. The above solvents may beused alone or in combination of two or more kinds thereof. Further, twokinds of the solvents which are not miscible with each other may beused.

Also, those described in the first invention apply as they are to theacid acceptor, the end terminating agent and the catalyst.

Further, those described in the first invention also apply as they areto the reaction conditions in the case of interfacial polymerization orthe reaction conditions in the case of transesterification.

Those described in the first invention also apply as they are to moldingand processing of the optical part-molding material comprising thearomatic polycarbonate resin thus obtained and various additives usedtherein.

The optical part-molding material of the present invention has anexcellent transparency and is excellent in a heat resistance, amechanical strength and a dimensional stability, and therefore it ishighly useful as a molding material for an optical disc substrate suchas a digital audio disc, a digital video disc and an optical memorydisc, various lenses such as a lens for an optical pickup, spectaclelenses, contact lenses and a lens sheet, an optical sheet substrate suchas a prism, a mirror, an optical fiber, a liquid crystal display and aportable key sheet and an optical functional element such as a lightguiding substance, a reflection film, a light scattering sheet, apolarizing plate and a phase difference plate.

Next, the present invention shall more specifically be explained withreference to examples and comparative examples.

EXAMPLE III-1

(1) Production of an Optical Part-Molding Material

Methylene chloride 700 ml which was a solvent was added to a solutionprepared by dissolving 45 g of 2,2-bis(4-hydroxyphenyl)adamantane and 25g of 1,1-bis(4-hydroxyphenyl)cyclohexane in 1,360 ml of a potassiumhydroxide aqueous solution having a concentration of 2 normal, andphosgene gas was blown into the above solution for 30 minutes in aproportion of 950 ml/minute under cooling while stirring. Then, thisreaction liquid was left standing still and separating, and a methylenechloride solution of an oligomer having a polymerization degree of 2 to5 and having a chloroformate group at a molecular end was obtained inthe organic layer.

Methylene chloride was added to 110 ml of the methylene chloridesolution thus obtained to control the whole amount to 150 ml, and then asolution prepared by dissolving 5 g of1,1-bis(4-hydroxyphenyl)cyclohexane in 50 ml of a potassium hydroxideaqueous solution having a concentration of 2 normal was added thereto.Further, 0.2 g of p-tert-butylphenol was added thereto as a molecularweight-controlling agent. Then, 1.0 ml of a triethylamine aqueoussolution having a concentration of 7% was added as a catalyst whilevigorously stirring the above mixed solution to carry out reaction at25° C. for 1.5 hour under stirring.

After finishing the reaction, the reaction product thus obtained wasdiluted with one liter of methylene chloride and washed twice with 1.5liter of water. Then, it was washed with hydrochloric acid having aconcentration of 0.05 normal and then further washed twice with oneliter of water. The organic layer thus obtained was thrown into methanolto carry out refining by reprecipitation, whereby a powder of anaromatic polycarbonate resin was obtained.

A solution of the aromatic polycarbonate resin obtained above having aconcentration of 0.5 g/liter using methylene chloride as a solvent had areduced viscosity (η_(sp)/c) of 0.6 deciliter/g at 20° C. Further,confirmation of the structure of the above aromatic polycarbonate resinby ¹H-NMR spectrum analysis resulted in finding that the chemicalstructure thereof comprised the following repetitive unit:

(2) Evaluation of the Optical Part-Molding Material

A solution having a concentration of 20 mass % which was prepared bydissolving the aromatic polycarbonate resin obtained in (1) describedabove in methylene chloride was cast on a glass substrate and leftstanding for a half day or longer, and then a film formed on the glasssubstrate was peeled off from the glass substrate. Then, this film washeated in a vacuum dryer at 70° C. for 2 hours and then at 100° C. for12 hours, whereby the transparent film having a thickness of 0.1 mm wasobtained.

(2-1) Heat Resistance

The aromatic polycarbonate resin film obtained above was heated from 25°C. up to 350° C. at a heating speed of 10° C./minute under nitrogen flow(20 ml/minute) by means of DSC220 manufactured by Seiko Electron Co.,Ltd. and immediately quenched to remove a heat history of the sample,and a glass transition temperature thereof was further measured at thesame heating speed according to JIS K7121. As a result thereof, it wasfound that the above aromatic polycarbonate resin had a glass transitiontemperature of 238° C.

(2-2) Transparency

A test piece having a length of 40 mm and a width of 40 mm was cut outfrom the aromatic polycarbonate resin film obtained above, and this testpiece was measured for a haze (%) by means of HGM-2DP type haze metermanufactured by Suga Test Instruments Co., Ltd. As a result thereof, itwas found that the above aromatic polycarbonate resin film had a haze of0.3%.

(2-3) Retardation

A test piece having a length of 40 mm and a width of 40 mm was cut outfrom the aromatic polycarbonate resin film obtained above, and this testpiece was measured for a phase difference at a wavelength of 15 nm bymeans of a polarizing microspectrophotometer by a rotary polarizermethod (Semonalmon method). As a result thereof, it was found that theabove aromatic polycarbonate resin film had a retardation of 4 nm.

(2-4) Refractive Index

A test piece having a length of 20 mm and a width of 10 mm was cut outfrom the aromatic polycarbonate resin film obtained above, and this testpiece was measured for a refractive index by means of an Abbe'srefractometer manufactured by Atago Co., Ltd. As a result thereof, itwas found that the above aromatic polycarbonate resin film had arefractive index of 1.584.

EXAMPLE III-2

(1) Production of an Optical Part-Molding Material

Methylene chloride 700 ml which was a solvent was added to a solutionprepared by dissolving 75 g of 2,2-bis(4-hydroxyphenyl)adamantane in1,360 ml of a potassium hydroxide aqueous solution having aconcentration of 2 normal, and phosgene gas was blown into the abovesolution for 30 minutes in a proportion of 950 ml/minute under coolingwhile stirring. Then, this reaction liquid was left standing still andseparating, and a methylene chloride solution of an oligomer having apolymerization degree of 2 to 5 and having a chloroformate group at amolecular end was obtained in the organic layer.

Methylene chloride was added to 110 ml of the methylene chloridesolution thus obtained to control the whole amount to 150 ml, and then asolution prepared by dissolving 6 g of9,9-bis(3-methyl-4-hydroxyphenyl)fluorene in 50 ml of a potassiumhydroxide aqueous solution having a concentration of 2 normal was addedthereto. Further, 0.2 g of p-tert-butylphenol was added thereto as amolecular weight-controlling agent. Then, 1.4 ml of a triethylamineaqueous solution having a concentration of 7% was added as a catalystwhile vigorously stirring the above mixed solution to carry out reactionat 25° C. for 1.5 hour under stirring.

After finishing the reaction, the reaction product thus obtained wasdiluted with 0.5 liter of methylene chloride and washed twice with 0.5liter of water. Then, it was washed with hydrochloric acid having aconcentration of 0.01 normal and then further washed twice with 0.5liter of water. The organic layer thus obtained was thrown into methanolto carry out refining by reprecipitation, whereby a powder of anaromatic polycarbonate resin was obtained.

A solution of the aromatic polycarbonate resin obtained above having aconcentration of 0.5 g/liter using methylene chloride as a solvent had areduced viscosity (η_(sp)/c) of 0.5 deciliter/g at 20° C. Further,confirmation of the structure of the above aromatic polycarbonate resinby ¹H-NMR spectrum analysis resulted in finding that the chemicalstructure thereof comprised the following repetitive unit:

(2) Evaluation of the Optical Part-Molding Material

The aromatic polycarbonate resin obtained in (1) described above wassubjected to the evaluation of an aromatic polycarbonate resin film inthe same manner as in (2) of Example III-1. The results thereof areshown in Table III-1.

EXAMPLE III-3

Methylene chloride 900 ml which was a solvent was added to a solutionprepared by dissolving 170 g of 1,1-bis(4-hydroxyphenyl)cyclohexane in1,530 ml of a potassium hydroxide aqueous solution having aconcentration of 2 normal, and phosgene gas was blown into the abovesolution for 30 minutes in a proportion of 950 ml/minute under coolingwhile stirring. Then, this reaction liquid was left standing still andseparating, and a methylene chloride solution of an oligomer having apolymerization degree of 2 to 5 and having a chloroformate group at amolecular end was obtained in the organic layer.

Methylene chloride was added to 110 ml of the methylene chloridesolution thus obtained to control the whole amount to 150 ml, and then asolution prepared by dissolving 6 g of2,2-bis(3,5-dimethyl-4-hydroxyphenyl)adamantane in 50 ml of a potassiumhydroxide aqueous solution having a concentration of 2 normal was addedthereto. Further, 0.2 g of p-tert-butylphenol was added thereto as amolecular weight-controlling agent. Then, 1.0 ml of a triethylamineaqueous solution having a concentration of 7% was added as a catalystwhile vigorously stirring the above mixed solution to carry out reactionat 25° C. for 1.5 hour under stirring.

After finishing the reaction, the reaction product thus obtained wasdiluted with 0.5 liter of methylene chloride and washed twice with 0.5liter of water. Then, it was washed with hydrochloric acid having aconcentration of 0.01 normal and then further washed twice with 0.5liter of water. The organic layer thus obtained was thrown into methanolto carry out refining by reprecipitation, whereby a powder of anaromatic polycarbonate resin was obtained.

A solution of the aromatic polycarbonate resin obtained above having aconcentration of 0.5 g/liter using methylene chloride as a solvent had areduced viscosity (n_(sp)/c) of 0.4 deciliter/g at 20° C. Further,confirmation of the structure of the above aromatic polycarbonate resinby ¹H-NMR spectrum analysis resulted in finding that the chemicalstructure thereof comprised the following repetitive unit:

(2) Evaluation of the Optical Part-Molding Material

The aromatic polycarbonate resin obtained in (1) described above wassubjected to the evaluation of the aromatic polycarbonate resin film inthe same manner as in (2) of Example III-1. The results thereof areshown in Table III-1.

COMPARATIVE EXAMPLE III-1

A film was obtained by the same casting method as in Example III-1,except that used was an aromatic polycarbonate resin (reduced viscosity(η_(sp)/c)=0.5 deciliter/g) produced by a publicly known interfacialpolymerization method using 2,2-bis(4-hydroxyphenyl)-propane as a rawmaterial. The aromatic polycarbonate resin obtained above was subjectedto the evaluation of an aromatic polycarbonate resin film in the samemanner as in (2) of Example III-1. The results thereof are shown inTable III-1 (in the table, ┌Example III-l┘ is shown as ┌Example 1┘ forconvenience, and the same shall apply to the other examples andcomparative examples). TABLE III-1 Example Comparative 1 2 3 Example 1Thickness (mm) 0.1 0.1 0.1 0.1 Glass 238 282 207 145 transitiontemperature (° C.) Retardation (nm) 4 3 5 11 Haze (%) 0.3 0.2 0.2 0.3Refractive index 1.584 1.590 1.578 1.585

INDUSTRIAL APPLICABILITY

According to the present invention, capable of being provided are anaromatic polycarbonate resin which is excellent in a transparency, aheat resistance and a mechanical strength and which has a goodmoldability, an effective production process for the same, an opticalpart-molding material which is excellent in an optical characteristicand a mechanical strength and which has a particularly high heatresistance and an optical part prepared by molding the same.

1. An aromatic polycarbonate resin which comprises a repetitive unit(I-1) represented by the following Formula (I-1):

(wherein R¹ represents a group selected from the group of a halogenatom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, anaryl-substituted alkenyl group having 7 to 13 carbon atoms and afluoroalkyl group having 1 to 6 carbon atoms; R² represents a groupselected from the group of a halogen atom, an alkyl group having 1 to 12carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl grouphaving 6 to 12 carbon atoms, an aryl-substituted alkenyl group having 7to 13 carbon atoms and a fluoroalkyl group having 1 to 12 carbon atoms;m represents an integer of 0 to 4; and n represents an integer of 0 to14) and a repetitive unit (I-2) represented by the following Formula(I-2):

(wherein R³ represents a group selected from the group of a halogenatom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, anaryl-substituted alkenyl group having 7 to 13 carbon atoms and afluoroalkyl group having 1 to 12 carbon atoms; X represents a singlebond, —O—, —CO—, —S—, —SO, —SO₂—, —C(R⁴R⁵)— (provided that R⁴ and R⁵each represent independently a hydrogen atom, an alkyl group having 1 to6 carbon atoms, a phenyl group or a trifluoromethyl group), asubstituted or non-substituted cycloalkylidene group having 6 to 12carbon atoms, a 9,9′-fluorenylidene group, a 1,8-menthanediyl group, a2,8-menthanediyl group, a substituted or non-substituted pyrazylidenegroup, a substituted or non-substituted arylene group having 6 to 12carbon atoms or—C(CH₃)₂-ph-C(CH₃)₂— (provided that ph represents aphenylene group); and p represents an integer of 0 to 4) and in whichthe solution having a concentration of 0.5 g/deciliter using methylenechloride as a solvent has a reduced viscosity (η_(sp)/c) of 0.1deciliter/g or more which is measured at 20° C.
 2. The aromaticpolycarbonate resin as described in claim 1, wherein the repetitive unit(I-2) is represented by the following Formula (I-3):

wherein R³, X and p each represent the same as R³, X and p in Formula(I-2).
 3. The aromatic polycarbonate resin as described in claim 1,wherein R¹ in Formula (I-1) is an alkyl group having 1 to 6 carbonatoms.
 4. The aromatic polycarbonate resin as described in claim 1,wherein X in Formula (I-2) is —C(R⁴R⁵)— (provided that R⁴ and R⁵ eachrepresent independently a hydrogen atom, an alkyl group having 1 to 6carbon atoms, a phenyl group or a trifluoromethyl group), a substitutedor non-substituted cycloalkylidene group having 6 to 12 carbon atoms ora 9,9′-fluorenylidene group.
 5. A production process for the aromaticpolycarbonate resin as described in claim 1, characterized by reacting a2,2-bis(4-hydroxyphenyl)adamantane compound represented by the followingFormula (I-4):

herein R¹ represents a group selected from the group of a halogen atom,an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6carbon atoms, an aryl group having 6 to 12 carbon atoms, anaryl-substituted alkenyl group having 7 to 13 carbon atoms and afluoroalkyl group having 1 to 6 carbon atoms; R² represents a groupselected from the group of a halogen atom, an alkyl group having 1 to 12carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl grouphaving 6 to 12 carbon atoms, an aryl-substituted alkenyl group having 7to 13 carbon atoms and a fluoroalkyl group having 1 to 12 carbon atoms;m represents an integer of 0 to 4; and n represents an integer of 0 to14) and divalent phenol represented by the following Formula (I-5):

(wherein R³ represents a group selected from the group of a halogenatom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, anaryl-substituted alkenyl group having 7 to 13 carbon atoms and afluoroalkyl group having 1 to 12 carbon atoms; X represents a singlebond, —O—, —CO—, —S—, —SO, —SO₂—, —C(R⁴R⁵)— (provided that R⁴ and R⁵each represent independently a hydrogen atom, an alkyl group having 1 to6 carbon atoms, a phenyl group or a trifluoromethyl group), asubstituted or non-substituted cycloalkylidene group having 6 to 12carbon atoms, a 9,9′-fluorenylidene group, a 1,8-menthanediyl group, a2,8-menthanediyl group, a substituted or non-substituted pyrazylidenegroup, a substituted or non-substituted arylene group having 6 to 12carbon atoms or —C(CH₃)₂-ph-C(CH₃)₂— (provided that ph represents aphenylene group); and p represents an integer of 0 to 4) with a carbonicester-forming compound.
 6. The production process for the aromaticpolycarbonate resin as described in claim 5, wherein a compoundrepresented by the following Formula (I-6) is used as the divalentphenol:

wherein R³, X and p each represent the same as R³, X and p in Formula(I-5).
 7. The production process for the aromatic polycarbonate resin asdescribed in claim 5, wherein the compound in which R¹ in Formula (I-4)is an alkyl group having 1 to 6 carbon atoms is used as the2,2-bis(4-hydroxyphenyl)adamantane compound.
 8. The production processfor the aromatic polycarbonate resin as described in claim 5, whereinused as the divalent phenol is the compound in which X in Formula (I-5)is —C(R⁴R⁵)—(provided that R⁴ and R⁵ each represent independently ahydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl groupor a trifluoromethyl group), a substituted or non-substitutedcycloalkylidene group having 6 to 12 carbon atoms or a9,9′-fluorenylidene group.
 9. An aromatic polycarbonate resin whichcomprises a repetitive unit represented by the following Formula (II-1):

wherein R¹ represents a group selected from the group of a halogen atom,an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6carbon atoms, an aryl group having 6 to 12 carbon atoms, anaryl-substituted alkenyl group having 7 to 13 carbon atoms and afluoroalkyl group having 1 to 6 carbon atoms; and m represents aninteger of 1 to 4) and in which the solution having a concentration of0.5 g/deciliter using methylene chloride as a solvent has a reducedviscosity (η_(sp)/c) of 0.1 deciliter/g or more which is measured at 20°C.
 10. The aromatic polycarbonate resin as described in claim 9, whereinR¹ in Formula (II-1) is an alkyl group having 1 to 6 carbon atoms. 11.An aromatic polycarbonate resin which comprises a repetitive unit (II-1)represented by the following Formula (II-2):

wherein R² represents a group selected from the group of a halogen atom,an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6carbon atoms, an aryl group having 6 to 12 carbon atoms, anaryl-substituted alkenyl group having 7 to 13 carbon atoms and afluoroalkyl group having 1 to 6 carbon atoms; and n is an integer of 1to 4) and a repetitive unit (II-2) represented by the following Formula(II-3):

(wherein R³ represents a group selected from the group of a halogenatom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, anaryl-substituted alkenyl group having 7 to 13 carbon atoms and afluoroalkyl group having 1 to 12 carbon atoms; and X represents a singlebond, —O—, —CO—, —S—, —SO—, —SO₂—, —C(R⁴R⁵)— (provided that R⁴ and R⁵each represent independently a hydrogen atom, an alkyl group having 1 to6 carbon atoms, a phenyl group or a trifluoromethyl group), asubstituted or non-substituted cycloalkylidene group having 6 to 12carbon atoms, a 9,9′-fluorenylidene group, a 1,8-menthanediyl group, a2,8-menthanediyl group, a substituted or non-substituted pyrazylidenegroup, a substituted or non-substituted arylene group having 6 to 12carbon atoms or —C(CH₃)₂-ph-C(CH₃)₂— (provided that ph represents aphenylene group); and p represents an integer of 0 to 4) and in whichthe solution having a concentration of 0.5 g/deciliter using methylenechloride as a solvent has a reduced viscosity (η_(sp)/c) of 0.1deciliter/g or more which is measured at 20° C.
 12. The aromaticpolycarbonate resin as described in claim 11, wherein the repetitiveunit (II-2) is represented by the following Formula (II-4):

wherein R³, X and p each represent the same as R³, X and p in Formula(II-3).
 13. The aromatic polycarbonate resin as described in claim 11,wherein R² in Formula (II-2) is an alkyl group having 1 to 6 carbonatoms.
 14. The aromatic polycarbonate resin as described in claim 11,wherein X in Formula (II-3) is —C(R⁴R⁵)— (provided that R⁴ and R⁵ eachrepresent independently a hydrogen atom, an alkyl group having 1 to 6carbon atoms, a phenyl group or a trifluoromethyl group), a substitutedor non-substituted cycloalkylidene group having 6 to 12 carbon atoms ora 9,9′-fluorenylidene group.
 15. A production process for the aromaticpolycarbonate resin as described in claim 9, characterized by reacting a1,3-bis(4-hydroxyphenyl)adamantane compound represented by the followingFormula (II-5):

(wherein R¹ represents a group selected from the group of a halogenatom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, anaryl-substituted alkenyl group having 7 to 13 carbon atoms and afluoroalkyl group having 1 to 6 carbon atoms; and m represents aninteger of 1 to 4) with a carbonic ester-forming compound.
 16. Theproduction process for the aromatic polycarbonate resin as described inclaim 15, wherein the compound in which R¹ in Formula (II-5) is an alkylgroup having 1 to 6 carbon atoms is used as the1,3-bis(4-hydroxyphenyl)adamantane compound.
 17. A production processfor the aromatic polycarbonate resin as described in claim 11,characterized by reacting a 1,3-bis(4-hydroxyphenyl)adamantane compoundrepresented by the following Formula (II-6):

(wherein R² represents a group selected from the group of a halogenatom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, anaryl-substituted alkenyl group having 7 to 13 carbon atoms and afluoroalkyl group having 1 to 6 carbon atoms; and n represents aninteger of 1 to 4) and divalent phenol represented by the followingFormula (II-7):

(wherein R³ represents a group selected from the group of a halogenatom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, anaryl-substituted alkenyl group having 7 to 13 carbon atoms and afluoroalkyl group having 1 to 12 carbon atoms; X represents a singlebond, —O—, —CO—, —S—, —SO, —SO₂—, —C(R⁴R⁵)— (provided that R⁴ and R⁵each represent independently a hydrogen atom, an alkyl group having 1 to6 carbon atoms, a phenyl group or a trifluoromethyl group), asubstituted or non-substituted cycloalkylidene group having 6 to 12carbon atoms, a 9,9′-fluorenylidene group, a 1,8-menthanediyl group, a2,8-menthanediyl group, a substituted or non-substituted pyrazylidenegroup, a substituted or non-substituted arylene group having 6 to 12carbon atoms or —C(CH₃)₂-ph-C(CH₃)₂— (provided that ph represents aphenylene group); and p represents an integer of 0 to 4) with a carbonicester-forming compound.
 18. The production process for the aromaticpolycarbonate resin as described in claim 17, wherein the compound inwhich R² in Formula (II-6) is an alkyl group having 1 to 6 carbon atomsis used as the 1,3-bis(4-hydroxyphenyl)adamantane compound.
 19. Theproduction process for the aromatic polycarbonate resin as described inclaim 17, wherein a compound represented by the following Formula (II-8)is used as the divalent phenol:

wherein R³, X and p each represent the same as R³, X and p in Formula(II-7).
 20. The production process for the aromatic polycarbonate resinas described in claim 17, wherein used as the divalent phenol is thecompound in which X in Formula (II-7) is —C(R⁴R⁵)—(provided that R⁴ andR⁵ each represent independently a hydrogen atom, an alkyl group having 1to 6 carbon atoms, a phenyl group or a trifluoromethyl group), asubstituted or non-substituted cycloalkylidene group having 6 to 12carbon atoms or a 9,9′-fluorenylidene group.
 21. An optical part-moldingmaterial comprising an aromatic polycarbonate resin which comprises arepetitive unit represented by the following Formula (III-1):

(wherein R¹ and R² each represent independently a group selected fromthe group of a halogen atom, an alkyl group having 1 to 6 carbon atoms,an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12carbon atoms, an aryl-substituted alkenyl group having 7 to 13 carbonatoms and a fluoroalkyl group having 1 to 6 carbon atoms; R³ representsa group selected from the group of a halogen atom, an alkyl group having1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, anaryl group having 6 to 12 carbon atoms, an aryl-substituted alkenylgroup having 7 to 13 carbon atoms and a fluoroalkyl group having 1 to 12carbon atoms; a and b represent an integer of 0 to 4; and c representsan integer of 0 to 14) and in which the solution having a concentrationof 0.5 g/deciliter using methylene chloride as a solvent has a reducedviscosity (η_(sp)/c) of 0.1 deciliter/g or more which is measured at 20°C.
 22. The optical part-molding material as described in claim 21,wherein R¹ and R² in Formula (III-1) are alkyl groups having 1 to 6carbon atoms.
 23. The optical part-molding material comprising thearomatic polycarbonate resin as described in claim 21, wherein therepetitive unit is represented by the following Formula (III-2):

wherein R¹, R², R³, a, b and c each represent the same as R¹, R², R³, a,b and c in Formula (III-1).
 24. The optical part-molding material asdescribed in claim 23, wherein R¹ and R² in Formula (III-2) are alkylgroups having 1 to 6 carbon atoms.
 25. An optical part-molding materialcomprising an aromatic polycarbonate resin which comprises a repetitiveunit (III-1) represented by the following Formula (III-3):

(wherein R⁴ and R⁵ each represent independently a group selected fromthe group of a halogen atom, an alkyl group having 1 to 6 carbon atoms,an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12carbon atoms, an aryl-substituted alkenyl group having 7 to 13 carbonatoms and a fluoroalkyl group having 1 to 6 carbon atoms; R⁶ representsa group selected from the group of a halogen atom, an alkyl group having1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, anaryl group having 6 to 12 carbon atoms, an aryl-substituted alkenylgroup having 7 to 13 carbon atoms and a fluoroalkyl group having 1 to 12carbon atoms; d and e represent an integer of 0 to 4; and f representsan integer of 0 to 14) and a repetitive unit (III-2) represented by thefollowing Formula (III-4):

(wherein R⁷ and R⁸ each represent independently a group selected fromthe group of a halogen atom, an alkyl group having 1 to 12 carbon atoms,an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to12 carbon atoms, an aryl-substituted alkenyl group having 7 to 13 carbonatoms and a fluoroalkyl group having 1 to 12 carbon atoms; X representsa single bond, —O—, —CO—, —S—, —SO—, —SO₂—, —C(R⁹R¹⁰)— (provided that R⁹and R¹⁰ each represent independently a hydrogen atom, an alkyl grouphaving 1 to 6 carbon atoms, a phenyl group or a trifluoromethyl group),a substituted or non-substituted cycloalkylidene group having 6 to 12carbon atoms, a 9,9′-fluorenylidene group, a 1,8-menthanediyl group, a2,8-menthanediyl group, a substituted or non-substituted pyrazylidenegroup, a substituted or non-substituted arylene group having 6 to 12carbon atoms, —C(CH₃)₂-ph-C(CH₃)₂—(provided that ph represents aphenylene group) or the following Formula (III-5) or (III-6):

(wherein R¹¹ and R¹² each represent independently a group selected fromthe group of a halogen atom, an alkyl group having 1 to 12 carbon atoms,an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to12 carbon atoms, an aryl-substituted alkenyl group having 7 to 13 carbonatoms and a fluoroalkyl group having 1 to 12 carbon atoms; and i and jeach represent an integer of 0 to 14); and g and h each represent aninteger of 0 to 4) and in which the solution having a concentration of0.5 g/deciliter using methylene chloride as a solvent has a reducedviscosity (η_(sp)/c) of 0.1 deciliter/g or more which is measured at 20°C.
 26. The optical part-molding material as described in claim 25,wherein R⁴ and R⁵ in Formula (III-3) are alkyl groups having 1 to 6carbon atoms.
 27. The optical part-molding material as described inclaim 25, wherein the repetitive unit (III-2) is represented by thefollowing Formula (III-7):

wherein R⁷, R⁸, X, g and h each represent the same as R⁷, R⁸, X, g and hin Formula (III-4).
 28. The optical part-molding material as describedin claim 25, wherein X in Formula (III-4) is —C(R⁹R¹⁰)— (provided thatR⁹ and R¹⁰ each represent independently a hydrogen atom, an alkyl grouphaving 1 to 6 carbon atoms, a phenyl group or a trifluoromethyl group),a substituted or non-substituted cycloalkylidene group having 6 to 12carbon atoms or a 9,9′-fluorenylidene group.
 29. An optical partprepared by molding the optical part-molding material as described inclaim 21.